Separating the Role of Protein Restraints and Local Metal-Site Interaction Chemistry in the Thermodynamics of a Zinc Finger Protein

PubMed Central

Dixit, Purushottam D.; Asthagiri, D.

2011-01-01

We express the effective Hamiltonian of an ion-binding site in a protein as a combination of the Hamiltonian of the ion-bound site in vacuum and the restraints of the protein on the site. The protein restraints are described by the quadratic elastic network model. The Hamiltonian of the ion-bound site in vacuum is approximated as a generalized Hessian around the minimum energy configuration. The resultant of the two quadratic Hamiltonians is cast into a pure quadratic form. In the canonical ensemble, the quadratic nature of the resultant Hamiltonian allows us to express analytically the excess free energy, enthalpy, and entropy of ion binding to the protein. The analytical expressions allow us to separate the roles of the dynamic restraints imposed by the protein on the binding site and the temperature-independent chemical effects in metal-ligand coordination. For the consensus zinc-finger peptide, relative to the aqueous phase, the calculated free energy of exchanging Zn2+ with Fe2+, Co2+, Ni2+, and Cd2+ are in agreement with experiments. The predicted excess enthalpy of ion exchange between Zn2+ and Co2+ also agrees with the available experimental estimate. The free energy of applying the protein restraints reveals that relative to Zn2+, the Co2+, and Cd2+-site clusters are more destabilized by the protein restraints. This leads to an experimentally testable hypothesis that a tetrahedral metal binding site with minimal protein restraints will be less selective for Zn2+ over Co2+ and Cd2+ compared to a zinc finger peptide. No appreciable change is expected for Fe2+ and Ni2+. The framework presented here may prove useful in protein engineering to tune metal selectivity. PMID:21943427

Capture of trace sulfur gases from binary mixtures by single-walled carbon nanotube arrays: a molecular simulation study.

PubMed

Wang, Wenjuan; Peng, Xuan; Cao, Dapeng

2011-06-01

Adsorption of H(2)S and SO(2) pure gases and their selective capture from the H(2)S-CH(4), H(2)S-CO(2), SO(2)-N(2), and SO(2)-CO(2) binary mixtures by the single-walled carbon nanotubes (SWNT) are investigated via using the grand canonical Monte Carlo (GCMC) method. It is found that the (20, 20) SWNT with larger diameter shows larger capacity for H(2)S and SO(2) pure gases at T = 303 K, in which the uptakes reach 16.31 and 16.03 mmol/g, respectively. However, the (6,6) SWNT with small diameter exhibits the largest selectivity for binary mixtures containing trace sulfur gases at T = 303 K and P = 100 kPa. By investigating the effect of pore size on the separation of gas mixtures, we found that the optimized pore size is 0.81 nm for separation of H(2)S-CH(4), H(2)S-CO(2), and SO(2)-N(2) binary mixtures, while it is 1.09 nm for the SO(2)-CO(2) mixture. The effects of concentration and temperature on the selectivity of sulfide are also studied at the optimal pore size. It is found that the concentration (ppm) of sulfur components has little effect on selectivity of SWNTs for these binary mixtures. However, the selectivity decreases obviously with the increase of temperature. To improve the adsorption capacities, we further modify the surface of SWNTs with the functional groups. The selectivities of H(2)S-CO(2) and SO(2)-CO(2) mixtures are basically uninfluenced by the site density, while the increase of site density can improve the selectivity of H(2)S-CH(4) mixture doubly. It is expected that this work could provide useful information for sulfur gas capture.

Directly converting CO2 into a gasoline fuel

PubMed Central

Wei, Jian; Ge, Qingjie; Yao, Ruwei; Wen, Zhiyong; Fang, Chuanyan; Guo, Lisheng; Xu, Hengyong; Sun, Jian

2017-01-01

The direct production of liquid fuels from CO2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na–Fe3O4/HZSM-5 catalyst, which can directly convert CO2 to gasoline-range (C5–C11) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe3O4, Fe5C2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO2 utilization to liquid fuels. PMID:28462925

Directly converting CO2 into a gasoline fuel.

PubMed

Wei, Jian; Ge, Qingjie; Yao, Ruwei; Wen, Zhiyong; Fang, Chuanyan; Guo, Lisheng; Xu, Hengyong; Sun, Jian

2017-05-02

The direct production of liquid fuels from CO 2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO 2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na-Fe 3 O 4 /HZSM-5 catalyst, which can directly convert CO 2 to gasoline-range (C 5 -C 11 ) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO 2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe 3 O 4 , Fe 5 C 2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO 2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO 2 utilization to liquid fuels.

In Situ Fabrication and Reactivation of Highly Selective and Stable Ag Catalysts for Electrochemical CO2 Conversion.

PubMed

Ma, Ming; Liu, Kai; Shen, Jie; Kas, Recep; Smith, Wilson A

2018-06-08

In this work, the highly selective and stable electrocatalytic reduction of CO 2 to CO on nanostructured Ag electrocatalysts is presented. The Ag electrocatalysts are synthesized by the electroreduction of Ag 2 CO 3 formed by in situ anodic-etching of Ag foil in a KHCO 3 electrolyte. After 3 min of this etching treatment, the Ag 2 CO 3 -derived nanostructured Ag electrocatalysts are capable of producing CO with up to 92% Faradaic efficiency at an overpotential as low as 290 mV, which surpasses all of the reported Ag catalysts at identical conditions to date. In addition, the anodic-etched Ag retained ∼90% catalytic selectivity in the electroreduction of CO 2 to CO for more than 100 h. The Ag 2 CO 3 -derived Ag is able to facilitate the activation of CO 2 via reduction of the activation energy barrier of the initial electron transfer and provide an increased number of active sites, resulting in the dramatically improved catalytic activity for the reduction of CO 2 to CO.

Transition Metal Ions in Zeolites: Coordination and activation of O2

PubMed Central

Smeets, Pieter J.; Woertink, Julia S.; Sels, Bert F.; Solomon, Edward I.; Schoonheydt, Robert A.

2010-01-01

Zeolites containing transition metal ions (TMI) often show promising activity as heterogeneous catalysts in pollution abatement and selective oxidation reactions. In this paper, two aspects of research on the TMI Cu, Co and Fe in zeolites are discussed: (i) coordination to the lattice and (ii) activated oxygen species. At low loading, TMI preferably occupy exchange sites in six-membered oxygen rings (6MR) where the TMI preferentially coordinate with the oxygen atoms of Al tetrahedra. High TMI loadings result in a variety of TMI species formed at the zeolite surface. Removal of the extra-lattice oxygens during high temperature pretreatments can result in auto-reduction. Oxidation of reduced TMI sites often results in the formation of highly reactive oxygen species. In Cu-ZSM-5, calcination with O2 results in the formation of a species, which was found to be a crucial intermediate in both the direct decomposition of NO and N2O and the selective oxidation of methane into methanol. An activated oxygen species, called α-oxygen, is formed in Fe-ZSM5 and reported to be the active site in the partial oxidation of methane and benzene into methanol and phenol, respectively. However, this reactive α-oxygen can only be formed with N2O, not with O2. O2 activated Co intermediates in Faujasite (FAU) zeolites can selectively oxidize α-pinene and epoxidize styrene. In Co-FAU, CoIII superoxo and peroxo complexes are suggested to be the active cores, whereas in Cu and Fe-ZSM-5 various monomeric and dimeric sites have been proposed, but no consensus has been obtained. Very recently, the active site in Cu-ZSM-5 was identified as a bent [Cu-O-Cu]2+ core (Proc. Natl. Acad. Sci. USA 2009, 106, 18908-18913). Overall, O2 activation depends on the interplay of structural factors such as type of zeolite, size of the channels and cages and chemical factors such as Si/Al ratio and the nature, charge and distribution of the charge balancing cations. The presence of several different TMI sites hinders the direct study of the spectroscopic features of the active site. Spectroscopic techniques capable of selectively probing these sites, even if they only constitute a minor fraction of the total amount of TMI sites, are thus required. Fundamental knowledge of the geometric and electronic structure of the reactive active site can help in the design of novel selective oxidation catalysts. PMID:20380459

On the relationship between ecosystem-scale hyperspectral reflectance and CO2 exchange in European mountain grasslands

NASA Astrophysics Data System (ADS)

Balzarolo, M.; Vescovo, L.; Hammerle, A.; Gianelle, D.; Papale, D.; Tomelleri, E.; Wohlfahrt, G.

2015-05-01

In this paper we explore the skill of hyperspectral reflectance measurements and vegetation indices (VIs) derived from these in estimating carbon dioxide (CO2) fluxes of grasslands. Hyperspectral reflectance data, CO2 fluxes and biophysical parameters were measured at three grassland sites located in European mountain regions using standardized protocols. The relationships between CO2 fluxes, ecophysiological variables, traditional VIs and VIs derived using all two-band combinations of wavelengths available from the whole hyperspectral data space were analysed. We found that VIs derived from hyperspectral data generally explained a large fraction of the variability in the investigated dependent variables but differed in their ability to estimate midday and daily average CO2 fluxes and various derived ecophysiological parameters. Relationships between VIs and CO2 fluxes and ecophysiological parameters were site-specific, likely due to differences in soils, vegetation parameters and environmental conditions. Chlorophyll and water-content-related VIs explained the largest fraction of variability in most of the dependent variables. Band selection based on a combination of a genetic algorithm with random forests (GA-rF) confirmed that it is difficult to select a universal band region suitable across the investigated ecosystems. Our findings have major implications for upscaling terrestrial CO2 fluxes to larger regions and for remote- and proximal-sensing sampling and analysis strategies and call for more cross-site synthesis studies linking ground-based spectral reflectance with ecosystem-scale CO2 fluxes.

DIAGNOSTIC MONITORING OF BIOGEOCHEMICAL INTERACTIONS OF A SHALLOW AQUIFER IN RESPONSE TO A CO2 LEAK

EPA Science Inventory

Results from these coupled laboratory and field experiments will greatly improve our understanding of the geochemical and microbiological reactions under low pH - high CO2 stress. We anticipate that this research will: (1) provide criteria for site selection for geological CO2...

High-performance multilayer composite membranes with mussel-inspired polydopamine as a versatile molecular bridge for CO2 separation.

PubMed

Li, Panyuan; Wang, Zhi; Li, Wen; Liu, Yanni; Wang, Jixiao; Wang, Shichang

2015-07-22

It is desirable to develop high-performance composite membranes for efficient CO2 separation in CO2 capture process. Introduction of a highly permeable polydimethylsiloxane (PDMS) intermediate layer between a selective layer and a porous support has been considered as a simple but efficient way to enhance gas permeance while maintaining high gas selectivity, because the introduced intermediate layer could benefit the formation of an ultrathin defect-free selective layer owing to the circumvention of pore penetration phenomenon. However, the selection of selective layer materials is unfavorably restricted because of the low surface energy of PDMS. Various highly hydrophilic membrane materials such as amino group-rich polyvinylamine (PVAm), a representative facilitated transport membrane material for CO2 separation, could not be facilely coated over the surface of the hydrophobic PDMS intermediate layer uniformly. Inspired by the hydrophilic nature and strong adhesive ability of polydopamine (PDA), PDA was therefore selected as a versatile molecular bridge between hydrophobic PDMS and hydrophilic PVAm. The PDA coating endows a highly compatible interface between both components with a large surface energy difference via multiple-site cooperative interactions. The resulting multilayer composite membrane with a thin facilitated transport PVAm selective layer exhibits a notably enhanced CO2 permeance (1887 GPU) combined with a slightly improved CO2/N2 selectivity (83), as well as superior structural stability. Similarly, the multilayer composite membrane with a hydrophilic CO2-philic Pebax 1657 selective layer was also developed for enhanced CO2 separation performance.

Biochemical Capture and Removal of Carbon Dioxide

NASA Technical Reports Server (NTRS)

Trachtenberg, Michael C.

1998-01-01

We devised an enzyme-based facilitated transport membrane bioreactor system to selectively remove carbon dioxide (CO2) from the space station environment. We developed and expressed site-directed enzyme mutants for CO2 capture. Enzyme kinetics showed the mutants to be almost identical to the wild type save at higher pH. Both native enzyme and mutant enzymes were immobilized to different supports including nylons, glasses, sepharose, methacrylate, titanium and nickel. Mutant enzyme could be attached and removed from metal ligand supports and the supports reused at least five times. Membrane systems were constructed to test CO2 selectivity. These included proteic membranes, thin liquid films and enzyme-immobilized teflon membranes. Selectivity ratios of more than 200:1 were obtained for CO2 versus oxygen with CO2 at 0.1%. The data indicate that a membrane based bioreactor can be constructed which could bring CO2 levels close to Earth.

3D-QSAR and molecular docking study on bisarylmaleimide series as glycogen synthase kinase 3, cyclin dependent kinase 2 and cyclin dependent kinase 4 inhibitors: an insight into the criteria for selectivity.

PubMed

Dessalew, Nigus; Bharatam, Prasad V

2007-07-01

Selective glycogen synthase kinase 3 (GSK3) inhibition over cyclin dependent kinases such as cyclin dependent kinase 2 (CDK2) and cyclin dependent kinase 4 (CDK4) is an important requirement for improved therapeutic profile of GSK3 inhibitors. The concepts of selectivity and additivity fields have been employed in developing selective CoMFA models for these related kinases. Initially, sets of three individual CoMFA models were developed, using 36 compounds of bisarylmaleimide series to correlate with the GSK3, CDK2 and CDK4 inhibitory potencies. These models showed a satisfactory statistical significance: CoMFA-GSK3 (r(2)(con), r(2)(cv): 0.931, 0.519), CoMFA-CDK2 (0.937, 0.563), and CoMFA-CDK4 (0.892, 0.725). Three different selective CoMFA models were then developed using differences in pIC(50) values. These three models showed a superior statistical significance: (i) CoMFA-Selective1 (r(2)(con), r(2)(cv): 0.969, 0.768), (ii) CoMFA-Selective 2 (0.974, 0.835) and (iii) CoMFA-Selective3 (0.963, 0.776). The selective models were found to outperform the individual models in terms of the quality of correlation and were found to be more informative in pinpointing the structural basis for the observed quantitative differences of kinase inhibition. An in-depth comparative investigation was carried out between the individual and selective models to gain an insight into the selectivity criterion. To further validate this approach, a set of new compounds were designed which show selectivity and were docked into the active site of GSK3, using FlexX based incremental construction algorithm.

CO2 time series patterns in contrasting headwater streams of North America

USGS Publications Warehouse

Crawford, John T.; Stanley, Emily H.; Dornblaser, Mark M.; Striegl, Robert G.

2017-01-01

We explored the underlying patterns of temporal stream CO2 partial pressure (pCO2) variability using highfrequency sensors in seven disparate headwater streams distributed across the northern hemisphere. We also compared this dataset of [40,000 pCO2 records with other published records from lotic systems. Individual stream sites exhibited relatively distinct pCO2 patterns over time with few consistent traits across sites. Some sites showed strong diel variability, some exhibited increasing pCO2 with increasing discharge, whereas other streams had reduced pCO2 with increasing discharge or no clear response to changes in flow. The only ‘‘universal’’ signature observed in headwater streams was a late summer pCO2 maxima that was likely driven by greatest rates of organic matter respiration due to highest annual temperatures. However, we did not observe this seasonal pattern in a southern hardwood forest site, likely because the region was transitioning from a severe drought. This work clearly illustrates the heterogeneous nature of headwater streams, and highlights the idiosyncratic nature of a non-conservative solute that is jointly influenced by physics, hydrology, and biology. We suggest that future researchers carefully select sensor locations (within and among streams) and provide additional contextual information when attempting to explain pCO2 patterns.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polster, C. S.; Zhang, R.; Cyb, M. T.

CO and H{sub 2} oxidation were studied over a series of Pt/CeO{sub 2} catalysts with differing Pt loadings and dispersions. Kinetic rate analysis confirms the presence of dual Langmuir-Hinshelwood (L-H) and Mars and van Krevelen (M-vK) pathways and is used to explain the loss in CO oxidation selectivity at low CO concentrations. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) shows the strong CO coverage dependence on both CO and O{sub 2} concentrations and explains the transition from L-H to M-vK reaction character. Redox site measurements are performed on Pt/CeO{sub 2} catalysts by anaerobic titrations under conditions where themore » M-vK pathway dominates the reaction rate. Similar redox site densities per interfacial Pt atom suggest that interfacial Pt-O-Ce sites are responsible for M-vK redox activity.« less

The long term trend of carbon dioxide and solar-induced chlorophyll fluorescence over selected sites using GOSAT target observation data

NASA Astrophysics Data System (ADS)

Kataoka, F.; Higuchi, R.; Kuze, A.; Shiomi, K.

2017-12-01

The Greenhouse gases Observing SATellite (GOSAT) is designed to measure the concentration of major greenhouse gases from space. GOSAT carry the Fourier-Transform Spectrometer, which have three shortwave infrared (SWIR) bands and one thermal infrared (TIR) band. The SWIR bands correspond to the O2A band (0.76 mm), weak-CO2 (1.6 mm) and strong-CO2 (2.0 mm). The SWIR bands observe the backscattered sunlight from surface and retrieve the column-averaged dry air mole fraction of carbon dioxide and methane. The 0.76 mm band can also detect the solar-induced chlorophyll fluorescence (SIF) using high spectral-resolution spectra in O2A band and solar absorption feature (Fraunhofer lines). GOSAT have operated more than 8 years and targeted various kinds of land-cover area (forest, grass, desert, etc.). The long term CO2 and SIF data set potential to address the rate of CO2 uptake through plant photosynthesis. In this work, we evaluated a trend and seasonal fluctuation components of CO2 and SIF using the liner and trigonometric functions fitting. We analyzed the amplitude and phase of the CO2 and SIF seasonal variation and anomalies over selected sites. Spatial distribution from target observation dataset which consist of 16 point per site using an agile pointing system over megacity is presented together with wind data. The data is available from the GOSAT trend viewer at http://www.eorc.jaxa.jp/GOSAT/CO2_monitor/.

A Triazole-Containing Metal-Organic Framework as a Highly Effective and Substrate Size-Dependent Catalyst for CO2 Conversion.

PubMed

Li, Pei-Zhou; Wang, Xiao-Jun; Liu, Jia; Lim, Jie Sheng; Zou, Ruqiang; Zhao, Yanli

2016-02-24

A highly porous metal-organic framework (MOF) incorporating both exposed metal sites and nitrogen-rich triazole groups was successfully constructed via solvothermal assembly of a clicked octcarboxylate ligand and Cu(II) ions, which presents a high affinity toward CO2 molecules clearly verified by gas adsorption and Raman spectral detection. The constructed MOF featuring CO2-adsorbing property and exposed Lewis-acid metal sites could serve as an excellent catalyst for CO2-based chemical fixation. Catalytic activity of the MOF was confirmed by remarkably high efficiency on CO2 cycloaddition with small epoxides. When extending the substrates to larger ones, its activity showed a sharp decrease. These observations reveal that MOF-catalyzed CO2 cycloaddition of small substrates was carried out within the framework, while large ones cannot easily enter into the porous framework for catalytic reactions. Thus, the synthesized MOF exhibits high catalytic selectivity to different substrates on account of the confinement of the pore diameter. The high efficiency and size-dependent selectivity toward small epoxides on catalytic CO2 cycloaddition make this MOF a promising heterogeneous catalyst for carbon fixation.

Unraveling the Nature of Active Sites in Ethanol Electro-oxidation by Site-Specific Marking of a Pt Catalyst with Isotope-Labeled 13CO.

PubMed

Farias, Manuel J S; Cheuquepán, William; Tanaka, Auro A; Feliu, Juan M

2018-03-15

This works deals with the identification of preferential site-specific activation at a model Pt surface during a multiproduct reaction. The (110)-type steps of a Pt(332) surface were selectively marked by attaching isotope-labeled 13 CO molecules to them, and ethanol oxidation was probed by in situ Foureir transfrom infrared spectroscopy in order to precisely determine the specific sites at which CO 2 , acetic acid, and acetaldehyde were preferentially formed. The (110) steps were active for splitting the C-C bond, but unexpectedly, we provide evidence that the pathway of CO 2 formation was preferentially activated at (111) terraces, rather than at (110) steps. Acetaldehyde was formed at (111) terraces at potentials comparable to those for CO 2 formation also at (111) terraces, while the acetic acid formation pathway became active only when the (110) steps were released by the oxidation of adsorbed 13 CO, at potentials higher than for the formation of CO 2 at (111) terraces of the stepped surface.

Selective Gas Capture Ability of Gas-Adsorbent-Incorporated Cellulose Nanofiber Films.

PubMed

Shah, Kinjal J; Imae, Toyoko

2016-05-09

The 2,2,6,6-tetramethylpiperidine-1-oxyl radical-oxidized cellulose nanofibers (TOCNF) were hybridized with cation and anion-exchange organoclays, where poly(amido amine) dendrimers were loaded to enhance the functionality of gas adsorption, since dendrimers have the high adsorbability and the enough selectivity on the gas adsorption. The thin films were prepared from the organoclay-TOCNF hybrids and supplied to the gas adsorption. The adsorption of CO2 and NH3 gases increased with an increasing amount of organoclays in TOCNF films, but the behavior of the increase depended on gases, clays, and dendrimers. The hydrotalcite organoclay-TOCNF films displayed the highest adsorption of both gases, but the desorption of CO2 gas from hydrotalcite organoclay-TOCNF films was drastically high in comparison with the other systems. While the CO2 gas is adsorbed and remained on cationic dendrimer sites in cation-exchange organoclay-TOCNF films, the CO2 gas is adsorbed on cationic clay sites in anion exchange organoclay-TOCNF films, and it is easily desorbed from the films. The NH3 adsorption is inversive to the CO2 adsorption. Then the CO2 molecules adsorbed on the cationic dendrimers and the NH3 molecules adsorbed on the anionic dendrimers are preferably captured in these adsorbents. The present research incorporated dendrimers will be contributing to the development of gas-specialized adsorbents, which are selectively storable only in particular gases.

Tuning Selectivity of CO 2 Hydrogenation Reactions at the Metal/Oxide Interface

DOE PAGES

Kattel, Shyam; Liu, Ping; Chen, Jingguang G.

2017-06-26

The chemical transformation of CO 2 not only mitigates the anthropogenic CO 2 emission into the Earth’s atmosphere but also produces carbon compounds that can be used as precursors for the production of chemicals and fuels. The activation and conversion of CO 2 can be achieved on multifunctional catalytic sites available at the metal/oxide interface by taking advantage of the synergy between the metal nanoparticles and oxide support. In this paper, we look at the recent progress in mechanistic studies of CO 2 hydrogenation to C1 (CO, CH 3OH, and CH 4) compounds on metal/oxide catalysts. On this basis, wemore » are able to provide a better understanding of the complex reaction network, grasp the capability of manipulating structure and combination of metal and oxide at the interface in tuning selectivity, and identify the key descriptors to control the activity and, in particular, the selectivity of catalysts. In conclusion, we also discuss challenges and future research opportunities for tuning the selective conversion of CO 2 on metal/oxide catalysts.« less

La-doped Al2O3 supported Au nanoparticles: highly active and selective catalysts for PROX under PEMFC operation conditions.

PubMed

Lin, Qingquan; Qiao, Botao; Huang, Yanqiang; Li, Lin; Lin, Jian; Liu, Xiao Yan; Wang, Aiqin; Li, Wen-Cui; Zhang, Tao

2014-03-14

La-doped γ-Al2O3 supported Au catalysts show high activity and selectivity for the PROX reaction under PEMFC operation conditions. The superior performance is attributed to the formation of LaAlO3, which suppresses H2 oxidation and strengthens CO adsorption on Au sites, thereby improving competitive oxidation of CO at elevated temperature.

Rules of co-occurring mutations characterize the antigenic evolution of human influenza A/H3N2, A/H1N1 and B viruses.

PubMed

Chen, Haifen; Zhou, Xinrui; Zheng, Jie; Kwoh, Chee-Keong

2016-12-05

The human influenza viruses undergo rapid evolution (especially in hemagglutinin (HA), a glycoprotein on the surface of the virus), which enables the virus population to constantly evade the human immune system. Therefore, the vaccine has to be updated every year to stay effective. There is a need to characterize the evolution of influenza viruses for better selection of vaccine candidates and the prediction of pandemic strains. Studies have shown that the influenza hemagglutinin evolution is driven by the simultaneous mutations at antigenic sites. Here, we analyze simultaneous or co-occurring mutations in the HA protein of human influenza A/H3N2, A/H1N1 and B viruses to predict potential mutations, characterizing the antigenic evolution. We obtain the rules of mutation co-occurrence using association rule mining after extracting HA1 sequences and detect co-mutation sites under strong selective pressure. Then we predict the potential drifts with specific mutations of the viruses based on the rules and compare the results with the "observed" mutations in different years. The sites under frequent mutations are in antigenic regions (epitopes) or receptor binding sites. Our study demonstrates the co-occurring site mutations obtained by rule mining can capture the evolution of influenza viruses, and confirms that cooperative interactions among sites of HA1 protein drive the influenza antigenic evolution.

CO2CARE - Site Closure Assessment Research - Recent Results

NASA Astrophysics Data System (ADS)

Wipki, Mario; Liebscher, Axel; Kühn, Michael; Lüth, Stefan; Durucan, Sevket; Deflandre, Jean-Pierre; Wollenweber, Jens; Chadwick, Andy; Böhm, Gualtiero

2013-04-01

The EU project CO2CARE, which started in January 2011, supports the large scale demonstration of CCS technology by addressing requirements of operators and regulators face in terms of CO2 storage site abandonment. The CO2CARE consortium, consisting of 24 project partners from universities, research institutes, and the industry, investigate technologies and procedures for abandonment and post-closure safety, satisfying the regulatory requirements for the transfer of responsibility. Nine key injections sites in Europe, USA, Japan, and Australia, each with a specific (hydro) geological and environmental character, were selected for investigations. These sites can be divided into the CO2 storage types on-shore, off-shore, natural CO2 reservoir, depleted gas reservoirs, and saline aquifers. The project mainly focuses on three key areas: - well abandonment and long-term integrity; - reservoir management and prediction from closure to the long-term; - risk management methodologies for long-term safety. These key areas are in turn closely linked to the three high-level requirements of the EU Directive 2009/31/EC, Article 18 for CO2 storage which are: (i) absence of any detectable leakage, (ii) conformity of actual behaviour of the injected CO2 with the modeled behaviour, and (iii) the storage site is evolving towards a situation of long-term stability. The identification of criteria and the development of site abandonment procedures and technologies, which guarantee the fulfillment of the high-level requirements, are the major objectives in CO2CARE. These criteria have to be fulfilled prior to subsequent transfer of responsibility to the competent authorities, typically 20 or 30 years after site closure. Finally, the essential results of the different working groups in CO2CARE will feed into overall guidelines for regulatory compliance and "Best Practice" for site abandonment. Dissemination of the results will show policy makers and the general public how site abandonment procedures for CO2 storage sites can be undertaken sustainably, cost-effectively and with no adverse effect to the local population and the natural environment. After more than two-thirds of the project`s lifetime, an overview of the project`s goals and the most relevant research findings are presented.

Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

2015-01-15

Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was moremore » beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.« less

Porous MOF with Highly Efficient Selectivity and Chemical Conversion for CO2.

PubMed

Wang, Hai-Hua; Hou, Lei; Li, Yong-Zhi; Jiang, Chen-Yu; Wang, Yao-Yu; Zhu, Zhonghua

2017-05-31

A new Co(II)-based MOF, {[Co 2 (tzpa)(OH)(H 2 O) 2 ]·DMF} n (1) (H 3 tzpa = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid), was constructed by employing a tetrazolyl-carboxyl ligand H 3 tzpa. 1 possesses 1D tubular channels that are decorated by μ 3 -OH groups, uncoordinated carboxylate O atoms, and open metal centers generated by the removal of coordinated water molecules, leading to high CO 2 adsorption capacity and significantly selective capture for CO 2 over CH 4 and CO in the temperature range of 298-333 K. Moreover, 1 shows the chemical stability in acidic and basic aqueous solutions. Grand canonical Monte Carlo simulations identified multiple CO 2 -philic sites in 1. In addition, the activated 1 as the heterogeneous Lewis and Brønsted acid bifunctional catalyst facilitates the chemical fixation of CO 2 coupling with epoxides into cyclic carbonates under ambient conditions.

The Sim-SEQ Project: Comparison of Selected Flow Models for the S-3 Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukhopadhyay, Sumit; Doughty, Christine A.; Bacon, Diana H.

Sim-SEQ is an international initiative on model comparison for geologic carbon sequestration, with an objective to understand and, if possible, quantify model uncertainties. Model comparison efforts in Sim-SEQ are at present focusing on one specific field test site, hereafter referred to as the Sim-SEQ Study site (or S-3 site). Within Sim-SEQ, different modeling teams are developing conceptual models of CO2 injection at the S-3 site. In this paper, we select five flow models of the S-3 site and provide a qualitative comparison of their attributes and predictions. These models are based on five different simulators or modeling approaches: TOUGH2/EOS7C, STOMP-CO2e,more » MoReS, TOUGH2-MP/ECO2N, and VESA. In addition to model-to-model comparison, we perform a limited model-to-data comparison, and illustrate how model choices impact model predictions. We conclude the paper by making recommendations for model refinement that are likely to result in less uncertainty in model predictions.« less

Health, Safety, and Environmental Screening and Ranking Frameworkfor Geologic CO2 Storage Site Selection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oldenburg, Curtis M.

2006-03-15

This report describes a screening and ranking framework(SRF) developed to evaluate potential geologic carbon dioxide (CO2)storage sites on the basis of health, safety, and environmental (HSE)risk arising from possible CO2 leakage. The approach is based on theassumption that HSE risk due to CO2 leakage is dependent on three basiccharacteristics of a geologic CO2 storage site: (1) the potential forprimary containment by the target formation, (2) the potential forsecondary containment if the primary formation leaks, and (3) thepotential for attenuation and dispersion of leaking CO2 if the primaryformation leaks and secondary containment fails. The framework isimplemented in a spreadsheet in whichmore » users enter numerical scoresrepresenting expert opinions or general information available frompublished materials along with estimates of uncertainty to evaluate thethree basic characteristics in order to screen and rank candidate sites.Application of the framework to the Rio Vista Gas Field, Ventura OilField, and Mammoth Mountain demonstrates the approach. Refinements andextensions are possible through the use of more detailed data or modelresults in place of property proxies. Revisions and extensions to improvethe approach are anticipated in the near future as it is used and testedby colleagues and collaborators.« less

Prospective CO 2 saline resource estimation methodology: Refinement of existing US-DOE-NETL methods based on data availability

DOE PAGES

Goodman, Angela; Sanguinito, Sean; Levine, Jonathan S.

2016-09-28

Carbon storage resource estimation in subsurface saline formations plays an important role in establishing the scale of carbon capture and storage activities for governmental policy and commercial project decision-making. Prospective CO 2 resource estimation of large regions or subregions, such as a basin, occurs at the initial screening stages of a project using only limited publicly available geophysical data, i.e. prior to project-specific site selection data generation. As the scale of investigation is narrowed and selected areas and formations are identified, prospective CO 2 resource estimation can be refined and uncertainty narrowed when site-specific geophysical data are available. Here, wemore » refine the United States Department of Energy – National Energy Technology Laboratory (US-DOE-NETL) methodology as the scale of investigation is narrowed from very large regional assessments down to selected areas and formations that may be developed for commercial storage. In addition, we present a new notation that explicitly identifies differences between data availability and data sources used for geologic parameters and efficiency factors as the scale of investigation is narrowed. This CO 2 resource estimation method is available for screening formations in a tool called CO 2-SCREEN.« less

Prospective CO 2 saline resource estimation methodology: Refinement of existing US-DOE-NETL methods based on data availability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goodman, Angela; Sanguinito, Sean; Levine, Jonathan S.

Carbon storage resource estimation in subsurface saline formations plays an important role in establishing the scale of carbon capture and storage activities for governmental policy and commercial project decision-making. Prospective CO 2 resource estimation of large regions or subregions, such as a basin, occurs at the initial screening stages of a project using only limited publicly available geophysical data, i.e. prior to project-specific site selection data generation. As the scale of investigation is narrowed and selected areas and formations are identified, prospective CO 2 resource estimation can be refined and uncertainty narrowed when site-specific geophysical data are available. Here, wemore » refine the United States Department of Energy – National Energy Technology Laboratory (US-DOE-NETL) methodology as the scale of investigation is narrowed from very large regional assessments down to selected areas and formations that may be developed for commercial storage. In addition, we present a new notation that explicitly identifies differences between data availability and data sources used for geologic parameters and efficiency factors as the scale of investigation is narrowed. This CO 2 resource estimation method is available for screening formations in a tool called CO 2-SCREEN.« less

A Decadal Inversion of CO2 Using the Global Eulerian-Lagrangian Coupled Atmospheric Model (GELCA): Sensitivity to the Ground-Based Observation Network

NASA Technical Reports Server (NTRS)

Shirai, T.; Ishizawa, M.; Zhuravlev, R.; Ganshin, A.; Belikov, D.; Saito, M.; Oda, T.; Valsala, V.; Gomez-Pelaez, A. J.; Langenfelds, R.;

Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance.

PubMed

Cheng, Tao; Xiao, Hai; Goddard, William A

2017-08-30

Recent experiments show that the grain boundaries (GBs) of copper nanoparticles (NPs) lead to an outstanding performance in reducing CO 2 and CO to alcohol products. We report here multiscale simulations that simulate experimental synthesis conditions to predict the structure of a 10 nm Cu NP (158 555 atoms). To identify active sites, we first predict the CO binding at a large number of sites and select four exhibiting CO binding stronger than the (211) step surface. Then, we predict the formation energy of the *OCCOH intermediate as a descriptor for C-C coupling, identifying two active sites, both of which have an under-coordinated surface square site adjacent to a subsurface stacking fault. We then propose a periodic Cu surface (4 by 4 supercell) with a similar site that substantially decreases the formation energy of *OCCOH, by 0.14 eV.

Moisture-Stable Zn(II) Metal-Organic Framework as a Multifunctional Platform for Highly Efficient CO2 Capture and Nitro Pollutant Vapor Detection.

PubMed

Chen, Di-Ming; Tian, Jia-Yue; Chen, Min; Liu, Chun-Sen; Du, Miao

2016-07-20

A moisture-stable three-dimensional (3D) metal-organic framework (MOF), {(Me2NH2)[Zn2(bpydb)2(ATZ)](DMA)(NMF)2}n (1, where bpydb = 4,4'-(4,4'-bipyridine-2,6-diyl)dibenzoate, ATZ = deprotonated 5-aminotetrazole, DMA = N,N-dimethylacetamide, and NMF = N-methylformamide), with uncoordinated N-donor sites and charged framework skeleton was fabricated. This MOF exhibits interesting structural dynamic upon CO2 sorption at 195 K and high CO2/N2 (127) and CO2/CH4 (131) sorption selectivity at 298 K and 1 bar. Particularly, its CO2/CH4 selectivity is among the highest MOFs for selective CO2 separation. The results of Grand Canonical Monte Carlo (GCMC) simulation indicate that the polar framework contributes to the strong framework-CO2 binding at zero loading, and the tetrazole pillar contributes to the high CO2 uptake capacity at high loading. Furthermore, the solvent-responsive luminescent properties of 1 indicate that it could be utilized as a fluorescent sensor to detect trace amounts of nitrobenzene in both solvent and vapor systems.

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2.

PubMed

Li, Wei; He, Da; Hu, Guoxiang; Li, Xiang; Banerjee, Gourab; Li, Jingyi; Lee, Shin Hee; Dong, Qi; Gao, Tianyue; Brudvig, Gary W; Waegele, Matthias M; Jiang, De-En; Wang, Dunwei

2018-05-23

The inertness of the C-H bond in CH 4 poses significant challenges to selective CH 4 oxidation, which often proceeds all the way to CO 2 once activated. Selective oxidation of CH 4 to high-value industrial chemicals such as CO or CH 3 OH remains a challenge. Presently, the main methods to activate CH 4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH 4 oxidation exhibit limited control over the product selectivity, with CO 2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH 4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO 2 grown by atomic layer deposition (ALD), which features high concentrations of Ti 3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO 2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO 2 . Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO 2 reduction mechanisms. Our results not only present a new route to selective CH 4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.

CO2 Separation and Capture Properties of Porous Carbonaceous Materials from Leather Residues

PubMed Central

Bermúdez, José M.; Dominguez, Pablo Haro; Arenillas, Ana; Cot, Jaume; Weber, Jens; Luque, Rafael

2013-01-01

Carbonaceous porous materials derived from leather skin residues have been found to have excellent CO2 adsorption properties, with interestingly high gas selectivities for CO2 (α > 200 at a gas composition of 15% CO2/85% N2, 273K, 1 bar) and capacities (>2 mmol·g−1 at 273 K). Both CO2 isotherms and the high heat of adsorption pointed to the presence of strong binding sites for CO2 which may be correlated with both: N content in the leather residues and ultrasmall pore sizes. PMID:28788352

Bipartite functions of the CREB co-activators selectively direct alternative splicing or transcriptional activation

PubMed Central

Amelio, Antonio L; Caputi, Massimo; Conkright, Michael D

2009-01-01

The CREB regulated transcription co-activators (CRTCs) regulate many biological processes by integrating and converting environmental inputs into transcriptional responses. Although the mechanisms by which CRTCs sense cellular signals are characterized, little is known regarding how CRTCs contribute to the regulation of cAMP inducible genes. Here we show that these dynamic regulators, unlike other co-activators, independently direct either pre-mRNA splice-site selection or transcriptional activation depending on the cell type or promoter context. Moreover, in other scenarios, the CRTC co-activators coordinately regulate transcription and splicing. Mutational analyses showed that CRTCs possess distinct functional domains responsible for regulating either pre-mRNA splicing or transcriptional activation. Interestingly, the CRTC1–MAML2 oncoprotein lacks the splicing domain and is incapable of altering splice-site selection despite robustly activating transcription. The differential usage of these distinct domains allows CRTCs to selectively mediate multiple facets of gene regulation, indicating that co-activators are not solely restricted to coordinating alternative splicing with increase in transcriptional activity. PMID:19644446

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kattel, Shyam; Liu, Ping; Chen, Jingguang G.

The chemical transformation of CO 2 not only mitigates the anthropogenic CO 2 emission into the Earth’s atmosphere but also produces carbon compounds that can be used as precursors for the production of chemicals and fuels. The activation and conversion of CO 2 can be achieved on multifunctional catalytic sites available at the metal/oxide interface by taking advantage of the synergy between the metal nanoparticles and oxide support. In this paper, we look at the recent progress in mechanistic studies of CO 2 hydrogenation to C1 (CO, CH 3OH, and CH 4) compounds on metal/oxide catalysts. On this basis, wemore » are able to provide a better understanding of the complex reaction network, grasp the capability of manipulating structure and combination of metal and oxide at the interface in tuning selectivity, and identify the key descriptors to control the activity and, in particular, the selectivity of catalysts. In conclusion, we also discuss challenges and future research opportunities for tuning the selective conversion of CO 2 on metal/oxide catalysts.« less

Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction.

PubMed

Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding

2017-08-28

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regional variability of grassland CO2 fluxes in Tyrol/Austria

NASA Astrophysics Data System (ADS)

Irschick, Christoph; Hammerle, Albin; Haslwanter, Alois; Wohlfahrt, Georg

2010-05-01

The FLUXNET project [1] aims at quantifying the magnitude and controls on the CO2, H2O and energy exchange of terrestrial ecosystems. Ideally, the various biomes of the Earth would be sampled in proportion to their spatial extent - in reality, however, study site selection is usually based on other (more practical) criteria so that a bias exists towards certain biomes and ecosystem types. This may be problematic because FLUXNET data are used to calibrate/parameterize models at various scales - if certain ecosystems are poorly replicated this may bias model predictions. Here we present data from a project in Tyrol/Austria where we have been investigating the CO2, H2O and energy exchange of five grassland sites during 2005-2007. The five permanent grassland sites were exposed to similar climate, but differed slightly in management. In a FLUXNET style approach, any of these sites might have been selected for making long-term flux measurements - the aim of this project was to examine the representativeness of these sites and, if evident, elucidate the causes for and controls on differences between sites. To this end we conducted continuous eddy covariance flux measurements at one (anchor) site [2, 3], and episodic, month long flux measurements at the four additional sites using a roving eddy covariance tower. These data were complemented by measurements of environmental drivers, the amount of above ground phytomass and basic data on vegetation and soil type, as well as management. Data are subject to a rigorous statistical analysis in order to quantify significant differences in the CO2, H2O and energy exchange between the sites and to identify the factors which are responsible for these differences. In the present contribution we report results on CO2 fluxes. Our major findings are that (i) site-identity of the surveyed grassland ecosystems was a significant factor for the net ecosystem CO2 exchange (NEE), somewhat less for gross primary production (GPP) and not for ecosystem respiration (RECO), (ii) GPP depended mainly on the amount of incident photosynthetically active radiation and the amount of green plant matter, the scale of influence of these two factors varying fourfold between the sites, and not so much on the available water, (iii) RECO was mainly affected by the soil temperature, but some evidence for priming effects was also found, (iv) the NEE was mainly influenced by GPP and to a lower extent by RECO. Taken together our results indicate that even within the same ecosystem type exposed to similar climate and land use, site selection may strongly affect the resulting NEE estimates. References: [1] D.D. Baldocchi, "Breathing of the terrestrial biosphere: lessons learned from a global network of carbon dioxide flux measurement systems", Australian Journal of Botany vol.56 (2008) pp. 1-26. [2] A. Hammerle, A. Haslwanter, U. Tappeiner, A. Cernusca, G. Wohlfahrt, "Leaf area controls on energy partitioning of a temperate mountain grassland", Biogeosciences vol.5 (2008) pp. 421 431. [3] G. Wohlfahrt, A. Hammerle, A. Haslwanter, M. Bahn, U. Tappeiner, A. Cernusca, "Seasonal and inter-annual variability of the net ecosystem CO2 exchange of a temperate mountain grassland: effects of weather and management", Journal of Geophysical Research 113 (2008) D08110, doi:10.1029/2007JD009286.

Health, Safety, and Environmental Screening and Ranking Frameworkfor Geologic CO2 Storage Site Selection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oldenburg, Curtis M.

2005-09-19

This report describes a screening and ranking framework(SRF) developed to evaluate potential geologic carbon dioxide (CO2) storage sites on the basis of health, safety, and environmental (HSE) risk arising from possible CO2 leakage. The approach is based on the assumption that HSE risk due to CO2 leakage is dependent on three basic characteristics of a geologic CO2 storage site: (1) the potential for primary containment by the target formation; (2) the potential for secondary containment if the primary formation leaks; and (3) the potential for attenuation and dispersion of leaking CO2 if the primary formation leaks and secondary containment fails.more » The framework is implemented in a spreadsheet in which users enter numerical scores representing expert opinions or general information available from published materials along with estimates of uncertainty to evaluate the three basic characteristics in order to screen and rank candidate sites. Application of the framework to the Rio Visa Gas Field, Ventura Oil Field, and Mammoth Mountain demonstrates the approach. Refinements and extensions are possible through the use of more detailed data or model results in place of property proxies. Revisions and extensions to improve the approach are anticipated in the near future as it is used and tested by colleagues and collaborators.« less

Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

PubMed

Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

2017-12-18

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geophysical Monitoring Methods Evaluation for the FutureGen 2.0 Project

DOE PAGES

Strickland, Chris E.; USA, Richland Washington; Vermeul, Vince R.; ...

2014-12-31

A comprehensive monitoring program will be needed in order to assess the effectiveness of carbon sequestration at the FutureGen 2.0 carbon capture and storage (CCS) field-site. Geophysical monitoring methods are sensitive to subsurface changes that result from injection of CO 2 and will be used for: (1) tracking the spatial extent of the free phase CO 2 plume, (2) monitoring advancement of the pressure front, (3) identifying or mapping areas where induced seismicity occurs, and (4) identifying and mapping regions of increased risk for brine or CO 2 leakage from the reservoir. Site-specific suitability and cost effectiveness were evaluated formore » a number of geophysical monitoring methods including: passive seismic monitoring, reflection seismic imaging, integrated surface deformation, time-lapse gravity, pulsed neutron capture logging, cross-borehole seismic, electrical resistivity tomography, magnetotellurics and controlled source electromagnetics. The results of this evaluation indicate that CO 2 injection monitoring using reflection seismic methods would likely be difficult at the FutureGen 2.0 site. Electrical methods also exhibited low sensitivity to the expected CO 2 saturation changes and would be affected by metallic infrastructure at the field site. Passive seismic, integrated surface deformation, time-lapse gravity, and pulsed neutron capture monitoring were selected for implementation as part of the FutureGen 2.0 storage site monitoring program.« less

Geophysical Monitoring Methods Evaluation for the FutureGen 2.0 Project

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strickland, Chris E.; USA, Richland Washington; Vermeul, Vince R.

A comprehensive monitoring program will be needed in order to assess the effectiveness of carbon sequestration at the FutureGen 2.0 carbon capture and storage (CCS) field-site. Geophysical monitoring methods are sensitive to subsurface changes that result from injection of CO 2 and will be used for: (1) tracking the spatial extent of the free phase CO 2 plume, (2) monitoring advancement of the pressure front, (3) identifying or mapping areas where induced seismicity occurs, and (4) identifying and mapping regions of increased risk for brine or CO 2 leakage from the reservoir. Site-specific suitability and cost effectiveness were evaluated formore » a number of geophysical monitoring methods including: passive seismic monitoring, reflection seismic imaging, integrated surface deformation, time-lapse gravity, pulsed neutron capture logging, cross-borehole seismic, electrical resistivity tomography, magnetotellurics and controlled source electromagnetics. The results of this evaluation indicate that CO 2 injection monitoring using reflection seismic methods would likely be difficult at the FutureGen 2.0 site. Electrical methods also exhibited low sensitivity to the expected CO 2 saturation changes and would be affected by metallic infrastructure at the field site. Passive seismic, integrated surface deformation, time-lapse gravity, and pulsed neutron capture monitoring were selected for implementation as part of the FutureGen 2.0 storage site monitoring program.« less

Effect of modification methods on the surface properties and n-butane isomerization performance of La/Ni-promoted SO42-/ZrO2-Al2O3

NASA Astrophysics Data System (ADS)

Wang, Pengzhao; Zhang, Jiaoyu; Han, Chaoyi; Yang, Chaohe; Li, Chunyi

2016-08-01

The La and/or Ni was introduced into alumina-promoted sulfated zirconia by impregnation and co-precipitation to improve the catalytic property of n-butane isomerization. Catalysts characterization shows that the addition of La/Ni has a remarkable influence on the surface and textual properties depending on the modification method. The impregnation of La/Ni facilitates the transformation of a small amount of tetragonal zirconia into monoclinic phase, while the co-precipitation improves the stability of tetragonal ZrO2. H2-TPR indicates that the addition of La/Ni changes the interaction between SO42- and supports, which affects the acidity on the surface. Specifically, the Lewis acidity is significantly enhanced by either modification method. The co-precipitation reserves almost all of the Brønsted acid sites, while the impregnation causes a remarkable decrease of Brønsted acid sites. Reaction results demonstrate that the co-precipitation exhibits a significant advantage over impregnation that the higher conversion of n-butane and selectivity to isobutane are obtained on the catalyst prepared by co-precipitation. The increase of catalytic activity is ascribed to the accelerated activation rate of n-butane molecules by hydride subtraction on the Lewis acid sites at higher reaction temperature. Furthermore, the addition of La/Ni improves the selectivity to isobutane by inhibiting the bimolecular reaction.

Photocatalytic reduction of CO2 to CO over copper decorated g-C3N4 nanosheets with enhanced yield and selectivity

NASA Astrophysics Data System (ADS)

Shi, Guodong; Yang, Lin; Liu, Zhuowen; Chen, Xiao; Zhou, Jianqing; Yu, Ying

2018-01-01

Photocatalytic reduction of CO2 to fuel has attracted considerable attention due to the consumption of fossil fuels and serious environmental problems. Although there are many photocatalysts reported for CO2 reduction, the improvement of activity and selectivity is still in great need of. In this work, a series of Cu nanoparticle decorated g-C3N4 nanosheets with different Cu loadings were fabricated by a facile secondary calcination and subsequent microwave hydrothermal method. The designed catalysts shown good photocatalytic activity and selectivity for CO2 reduction to CO. The optimal sample exhibited a 3-fold augmentation of the CO yield in comparison with pristine g-C3N4 under visible light. It is revealed that with the loading of Cu nanoparticles, the resulting photocatalyst possessed an improved charge carrier transfer and separation efficiency as well as increased surface reactive sites, resulting in a significant enhancement of CO yield. It is anticipated that the designed Cu/C3N4 photocatalyst may provide new insights for two dimensional layer materials and non-noble particles applied to CO2 reduction.

Evaluating Impacts of CO2 and CH4 Gas Intrusion into an Unconsolidated Aquifer: Fate of As and Cd

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawter, Amanda R.; Qafoku, Nikolla; Shao, Hongbo

2015-07-10

Abstract The sequestration of carbon dioxide (CO2) in deep underground reservoirs has been identified as an important strategy to decrease atmospheric CO2 levels and mitigate global warming, but potential risks on overlying aquifers currently lack a complete evaluation. In addition to CO2, other gases such as methane (CH4) may be present in storage reservoirs. This paper explores for the first time the combined effect of leaking CO2 and CH4 gasses on the fate of major, minor and trace elements in an aquifer overlying a potential sequestration site. Emphasis is placed on the fate of arsenic (As) and cadmium (Cd) releasedmore » from the sediments or present as soluble constituents in the leaking brine. Results from macroscopic batch and column experiments show that the presence of CH4 (at a concentration of 1 % in the mixture CO2/CH4) does not have a significant effect on solution pH or the concentrations of most major elements (such as Ca, Ba, and Mg). However, the concentrations of Mn, Mo, Si and Na are inconsistently affected by the presence of CH4 (i.e., in at least one sediment tested in this study). Cd is not released from the sediments and spiked Cd is mostly removed from the aqueous phase most likely via adsorption. The fate of sediment associated As [mainly sorbed arsenite or As(III) in minerals] and spiked As [i.e., As5+] is complex. Possible mechanisms that control the As behavior in this system are discussed in this paper. Results are significant for CO2 sequestration risk evaluation and site selection and demonstrate the importance of evaluating reservoir brine and gas stream composition during site selection to ensure the safest site is being chosen.« less

DFT analysis of the reaction paths of formaldehyde decomposition on silver.

PubMed

Montoya, Alejandro; Haynes, Brian S

2009-07-16

Periodic density functional theory is used to study the dehydrogenation of formaldehyde (CH(2)O) on the Ag(111) surface and in the presence of adsorbed oxygen or hydroxyl species. Thermodynamic and kinetic parameters of elementary surface reactions have been determined. The dehydrogenation of CH(2)O on clean Ag(111) is thermodynamically and kinetically unfavorable. In particular, the activation energy for the first C-H bond scission of adsorbed CH(2)O (25.8 kcal mol(-1)) greatly exceeds the desorption energy for molecular CH(2)O (2.5 kcal mol(-1)). Surface oxygen promotes the destruction of CH(2)O through the formation of CH(2)O(2), which readily decomposes to CHO(2) and then in turn to CO(2) and adsorbed hydrogen. Analysis of site selectivity shows that CH(2)O(2), CHO(2), and CHO are strongly bound to the surface through the bridge sites, whereas CO and CO(2) are weakly adsorbed with no strong preference for a particular surface site. Dissociation of CO and CO(2) on the Ag(111) surface is highly activated and therefore unfavorable with respect to their molecular desorption.

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

DOE PAGES

Gulliver, Djuna M.; Lowry, Gregory V.; Gregory, Kelvin B.

2016-08-09

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2. Microbial community change in these subsurface sites may affect injectivity of CO 2, permanence of stored CO 2, and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%,more » and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2-exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2-selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2-exposed environments.« less

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna M.; Lowry, Gregory V.; Gregory, Kelvin B.

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2. Microbial community change in these subsurface sites may affect injectivity of CO 2, permanence of stored CO 2, and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%,more » and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2-exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2-selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2-exposed environments.« less

A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol

PubMed Central

Wang, Jijie; Li, Guanna; Li, Zelong; Tang, Chizhou; Feng, Zhaochi; An, Hongyu; Liu, Hailong; Liu, Taifeng; Li, Can

2017-01-01

Although methanol synthesis via CO hydrogenation has been industrialized, CO2 hydrogenation to methanol still confronts great obstacles of low methanol selectivity and poor stability, particularly for supported metal catalysts under industrial conditions. We report a binary metal oxide, ZnO-ZrO2 solid solution catalyst, which can achieve methanol selectivity of up to 86 to 91% with CO2 single-pass conversion of more than 10% under reaction conditions of 5.0 MPa, 24,000 ml/(g hour), H2/CO2 = 3:1 to 4:1, 320° to 315°C. Experimental and theoretical results indicate that the synergetic effect between Zn and Zr sites results in the excellent performance. The ZnO-ZrO2 solid solution catalyst shows high stability for at least 500 hours on stream and is also resistant to sintering at higher temperatures. Moreover, no deactivation is observed in the presence of 50 ppm SO2 or H2S in the reaction stream. PMID:28989964

Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

NASA Astrophysics Data System (ADS)

Wang, Yuting; Deutscher, Nicholas M.; Palm, Mathias; Warneke, Thorsten; Notholt, Justus; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Jones, Nicholas; Mahieu, Emmanuel; Lejeune, Bernard; Hannigan, James; Conway, Stephanie; Mendonca, Joseph; Strong, Kimberly; Campbell, J. Elliott; Wolf, Adam; Kremser, Stefanie

2016-02-01

Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world.

Adsorption Properties of MFM-400 and MFM-401 with CO2 and Hydrocarbons: Selectivity Derived from Directed Supramolecular Interactions.

PubMed

Ibarra, Ilich A; Mace, Amber; Yang, Sihai; Sun, Junliang; Lee, Sukyung; Chang, Jong-San; Laaksonen, Aatto; Schröder, Martin; Zou, Xiaodong

2016-08-01

([Sc2(OH)2(BPTC)]) (H4BPTC = biphenyl-3,3',5,5'-tetracarboxylic acid), MFM-400 (MFM = Manchester Framework Material, previously designated NOTT), and ([Sc(OH)(TDA)]) (H2TDA = thiophene-2,5-dicarboxylic acid), MFM-401, both show selective and reversible capture of CO2. In particular, MFM-400 exhibits a reasonably high CO2 uptake at low pressures and competitive CO2/N2 selectivity coupled to a moderate isosteric heat of adsorption (Qst) for CO2 (29.5 kJ mol(-1)) at zero coverage, thus affording a facile uptake-release process. Grand canonical Monte Carlo (GCMC) and density functional theory (DFT) computational analyses of CO2 uptake in both materials confirmed preferential adsorption sites consistent with the higher CO2 uptake observed experimentally for MFM-400 over MFM-401 at low pressures. For MFM-400, the Sc-OH group participates in moderate interactions with CO2 (Qst = 33.5 kJ mol(-1)), and these are complemented by weak hydrogen-bonding interactions (O···H-C = 3.10-3.22 Å) from four surrounding aromatic -CH groups. In the case of MFM-401, adsorption is provided by cooperative interactions of CO2 with the Sc-OH group and one C-H group. The binding energies obtained by DFT analysis for the adsorption sites for both materials correlate well with the observed moderate isosteric heats of adsorption for CO2. GCMC simulations for both materials confirmed higher uptake of EtOH compared with nonpolar vapors of toluene and cyclohexane. This is in good correlation with the experimental data, and DFT analysis confirmed the formation of a strong hydrogen bond between EtOH and the hydrogen atom of the hydroxyl group of the MFM-400 and MFM-401 framework (FW) with H-OEtOH···H-OFW distances of 1.77 and 1.75 Å, respectively. In addition, the accessible regeneration of MFM-400 and MFM-401 and release of CO2 potentially provide minimal economic and environmental penalties.

A gap-filling model for eddy covariance CO2 flux: Estimating carbon assimilated by a subtropical evergreen broad-leaved forest at the Lien-Hua-Chih flux observation site

NASA Astrophysics Data System (ADS)

Lan, C. Y.; Li, M. H.; Chen, Y. Y.

2016-12-01

Appropriate estimations of gaps appeared in eddy covariance (EC) flux observations are critical to the reliability of long-term EC applications. In this study we present a semi-parametric multivariate gap-filling model for tower-based measurement of CO2 flux. The raw EC data passing QC/QA was separated into two groups, clear sky, having net radiation greater than 50 W/m2, and nighttime/cloudy. For the clear sky conditions, the principle component analysis (PCA) was used to resolve the multicollinearity relationships among various environmental variables, including net radiation, wind speed, vapor pressure deficit, soil moisture deficit, leaf area index, and soil temperature, in association with CO2 assimilated by forest. After the principal domains were determined by the PCA, the relationships between CO2 fluxes and selected PCs (key factors) were built up by nonlinear interpolations to estimate the gap-filled CO2 flux. In view of limited photosynthesis at nighttime/cloudy conditions, respiration rate of the forest ecosystem was estimated by the Lloyd-Tylor equation. Artificial gaps were randomly selected to exam the applicability of our PCA approach. Based on tower-based measurement of CO2 flux at the Lien-Hua-Chih site, a total of 5.8 ton-C/ha/yr was assimilated in 2012.

The Effect of Surface Site Ensembles on the Activity and Selectivity of Ethanol Electrooxidation by Octahedral PtNiRh Nanoparticles.

PubMed

Erini, Nina; Beermann, Vera; Gocyla, Martin; Gliech, Manuel; Heggen, Marc; Dunin-Borkowski, Rafal E; Strasser, Peter

2017-06-01

Direct ethanol fuel cells are attractive power sources based on a biorenewable, high energy-density fuel. Their efficiency is limited by the lack of active anode materials which catalyze the breaking of the C-C bond coupled to the 12-electron oxidation to CO 2 . We report shape-controlled PtNiRh octahedral ethanol oxidation electrocatalysts with excellent activity and previously unachieved low onset potentials as low as 0.1 V vs. RHE, while being highly selective to complete oxidation to CO 2 . Our comprehensive characterization and in situ electrochemical ATR studies suggest that the formation of a ternary surface site ensemble around the octahedral Pt 3 Ni 1 Rh x nanoparticles plays a crucial mechanistic role for this behavior. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dialing in single-site reactivity of a supported calixarene-protected tetrairidium cluster catalyst† †Electronic supplementary information (ESI) available: Detailed characterization of Ir4 clusters, raw kinetic data, time scale analysis, experimental methods, and sample preparation. See DOI: 10.1039/c7sc00686a Click here for additional data file.

PubMed Central

Palermo, Andrew; Solovyov, Andrew; Ertler, Daniel

2017-01-01

A closed Ir4 carbonyl cluster, 1, comprising a tetrahedral metal frame and three sterically bulky tert-butyl-calix[4]arene(OPr)3(OCH2PPh2) (Ph = phenyl; Pr = propyl) ligands at the basal plane, was characterized with variable-temperature 13C NMR spectroscopy, which show the absence of scrambling of the CO ligands at temperatures up to 313 K. This demonstration of distinct sites for the CO ligands was found to extend to the reactivity and catalytic properties, as shown by selective decarbonylation in a reaction with trimethylamine N-oxide (TMAO) as an oxidant, which, reacting in the presence of ethylene, leads to the selective bonding of an ethyl ligand at the apical Ir site. These clusters were supported intact on porous silica and found to catalyze ethylene hydrogenation, and a comparison of the kinetics of the single-hydrogenation reaction and steady-state hydrogenation catalysis demonstrates a unique single-site catalyst—with each site having the same catalytic activity. Reaction orders in the catalytic ethylene hydrogenation reaction of approximately 1/2 and 0 for H2 and C2H4, respectively, nearly match those for conventional noble-metal catalysts. In contrast to oxidative decarbonylation, thermal desorption of CO from silica-supported cluster 1 occurred exclusively at the basal plane, giving rise to sites that do not react with ethylene and are catalytically inactive for ethylene hydrogenation. The evidence of distinctive sites on the cluster catalyst leads to a model that links to hydrogen-transfer catalysis on metals—involving some surface sites that bond to both hydrocarbon and hydrogen and are catalytically engaged (so-called “*” sites) and others, at the basal plane, which bond hydrogen and CO but not hydrocarbon and are reservoir sites (so-called “S” sites). PMID:28959418

Evaluation of National Atmospheric Deposition Program measurements for co-located Sites CO89 and CO98 at Rocky Mountain National Park, 2012

USGS Publications Warehouse

,

2013-01-01

Median weekly absolute percent differences for selected parameters including: sample volume, 8.0 percent; ammonium concentration, 9.1 percent; nitrate concentration, 8.5 percent; sulfate concentration, 10.2 percent. Annual precipitation-weighted mean concentrations were higher for CO98 compared to CO89 for all analytes. The chemical concentration record for CO98 contains more valid samples than the CO89 record. Therefore, the CO98 record is more representative of 2012 total annual deposition at Loch Vale. Daily precipitation-depth records for the co-located precipitation gages were 100 percent complete, and the total annual precipitation depths between the sites differed by 0.1 percent for the year (91.5 and 91.4 cm).

CO adsorption on ion bombarded Ni(111): characterization by photoemission from adsorbed xenon

NASA Astrophysics Data System (ADS)

Fu, Sabrina S.; Malafsky, Geoffrey P.; Hsu, David S. Y.

1993-11-01

The adsorption of CO on Ni(111), ion bombarded with various fluences of 1.0 keV Ar + ions, has been investigated using photoemission from adsorbed xenon (PAX). After ion bombardment of the Ni(111) surface, various amounts of CO were adsorbed, followed by adsorption of xenon at 85 K. Two pressures of xenon were used in examining the 3d {5}/{2} peak of xenon: 5 × 10 -6 and 7 × 10 -10 Torr. PAX data taken at both pressures show that CO selectively adsorbs onto the defect (step) sites created by ion bombardment. In addition, it was found that the amount of CO which could occupy a defect site previously occupied by one Xe atom varied from 10 to 2.5, depending on the ion fluence.

Emerging materials for lowering atmospheric carbon

DOE PAGES

Barkakaty, Balaka; Sumpter, Bobby G.; Ivanov, Ilia N.; ...

2016-12-08

CO 2 emissions from anthropogenic sources and the rate at which they increase could have deep global ramifications such as irreversible climate change and increased natural disasters. Because greater than 50% of anthropogenic CO 2 emissions come from small, distributed sectors such as homes, offices, and transportation sources, most renewable energy systems and on-site carbon capture technologies for reducing future CO 2 emissions cannot be effectively utilized. This problem might be mediated by considering novel materials and technologies for directly capturing/removing CO 2 from air. But, compared to materials for capturing CO 2 at on-site emission sources, materials for capturingmore » CO 2 directly from air must be more selective to CO 2, and should operate and be stable at near ambient conditions. Here, we briefly summarize the recent developments in materials for capturing carbon dioxide directly from air. Furthermore, we discuss the challenges in this field and offer a perspective for developing the current state-of-art and also highlight the potential of a few recent discoveries in materials science that show potential for advanced application of air capture technology.« less

CO2 sequestration in two mediterranean dune areas subjected to a different level of anthropogenic disturbance

NASA Astrophysics Data System (ADS)

Bonito, Andrea; Ricotta, Carlo; Iberite, Mauro; Gratani, Loretta; Varone, Laura

2017-09-01

Coastal sand dunes are among the most threatened habitats, especially in the Mediterranean Basin, where the high levels of human pressure impair the presence of plant species, putting at risk the maintenance of the ecosystem services, such as CO2 sequestration provided by these habitats. The aim of this study was to analyze how disturbance-induced changes in plant species abundance patterns account for variations in annual CO2 sequestration flow (CS) of Mediterranean sand dune areas. Two sites characterized by a high (site HAD) and a lower (site LAD) anthropogenic disturbance level were selected. At both sites, plant species number, cover, height and CS based on net photosynthesis measurements were sampled. At the plant species level, our results highlighted that Ammophila arenaria and Pancratium maritimum, had a key role in CS. Moreover, the results revealed a patchy species assemblage in both sites. In particular, HAD was characterized by a higher extension of the anthropogenic aphytoic zone (64% of the total transect length) than LAD. In spite of the observed differences in plant species composition, there were not significant differences between HAD and LAD in structural and functional traits, such as plant height and net photosynthesis. As a consequence, HAD and LAD had a similar CS (443 and 421 Mg CO2 ha-1 y-1, respectively). From a monetary point of view, our estimates based on the social costs of carbon revealed that the flow of sequestered CO2 valued on an average 3181 ± 114 ha-1 year-1 (mean value for the two sites). However, considering also the value of the CO2 negative flow related to loss of vegetated area, the annual net benefit arising from CO2 sequestration amounted to 1641 and 1772 for HAD and LAD, respectively. Overall, the results highlighted the importance to maximize the efforts to preserve dune habitats by applying an effective management policy, which could allow maintaining also a regulatory ecosystem service such as CO2 sequestration.

US EPA Base Study Standard Operating Procedure for Continuous Monitoring of Indoor Air

EPA Pesticide Factsheets

The procedure described is intended for monitoring continuously and simultaneously, at selected work sites, parameters that are most commonly associated with the quality of indoor environments: the concentrations of carbon dioxide (CO2), carbon monoxide (CO), temperature, relative humidity (RH), illumination, and noise.

Selective carbon dioxide sorption by a new breathing three-dimensional Zn-MOF with Lewis basic nitrogen-rich channels.

PubMed

Kim, Hyun-Chul; Huh, Seong; Lee, Do Nam; Kim, Youngmee

2018-04-03

Lewis basic heteroatoms orderly located inside the well-defined channels of metal-organic frameworks (MOFs) are potentially ideal active sites for selective gas sorption and catalysis. To develop functional MOFs with Lewis basic sites inside channels, a new C2h-symmetric dicarboxylate-based bridging ligand, 3,3'-(pyrazine-2,5-diyl)dibenzoic acid (3,3'-PDBA), was prepared by a Suzuki coupling reaction. Subsequently, two new Zn-MOFs containing the C2h-symmetric 3,3'-PDBA bridging ligand and two different bis(pyridyl)-based pillars, 1,2-bis(4-pyridyl)ethane (bpa) or 1,2-bis(4-pyridyl)ethylene (bpe), were prepared through a thermal reaction in N,N-dimethylformamide (DMF). The resulting two Zn-MOFs of the general formula of three-dimensional (3D) [Zn2(μ4-3,3'-PDBA)2(μ2-bpa)]3·(DMF)5(H2O)13 (1) or 3D-like 2D [Zn2(μ4-3,3'-PDBA)2(μ2-bpe)]·(H2O) (2) displayed primitive cubic pcu net and 2D sql net, respectively. Both Zn-MOFs 1 and 2 contain uncoordinated Lewis basic pyrazinyl nitrogen atoms in the frameworks. The solvent-free 1 with flexible bpa linkers only showed a potential porosity of 15.9% by PLATON analysis. Zn-MOF 1 with openly accessible Lewis basic sites exhibited selective sorption of CO2 over N2, H2, and CH4 at low temperature. The adsorption and desorption isotherms for CO2 sorption at 196 K showed phenomenal hysteretic behaviour indicative of a breathing process through an adsorbate-discriminatory gate-opening process toward CO2 at a low gas pressure.

Modeling and Evaluation of Geophysical Methods for Monitoring and Tracking CO2 Migration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniels, Jeff

2012-11-30

Geological sequestration has been proposed as a viable option for mitigating the vast amount of CO{sub 2} being released into the atmosphere daily. Test sites for CO{sub 2} injection have been appearing across the world to ascertain the feasibility of capturing and sequestering carbon dioxide. A major concern with full scale implementation is monitoring and verifying the permanence of injected CO{sub 2}. Geophysical methods, an exploration industry standard, are non-invasive imaging techniques that can be implemented to address that concern. Geophysical methods, seismic and electromagnetic, play a crucial role in monitoring the subsurface pre- and post-injection. Seismic techniques have beenmore » the most popular but electromagnetic methods are gaining interest. The primary goal of this project was to develop a new geophysical tool, a software program called GphyzCO2, to investigate the implementation of geophysical monitoring for detecting injected CO{sub 2} at test sites. The GphyzCO2 software consists of interconnected programs that encompass well logging, seismic, and electromagnetic methods. The software enables users to design and execute 3D surface-to-surface (conventional surface seismic) and borehole-to-borehole (cross-hole seismic and electromagnetic methods) numerical modeling surveys. The generalized flow of the program begins with building a complex 3D subsurface geological model, assigning properties to the models that mimic a potential CO{sub 2} injection site, numerically forward model a geophysical survey, and analyze the results. A test site located in Warren County, Ohio was selected as the test site for the full implementation of GphyzCO2. Specific interest was placed on a potential reservoir target, the Mount Simon Sandstone, and cap rock, the Eau Claire Formation. Analysis of the test site included well log data, physical property measurements (porosity), core sample resistivity measurements, calculating electrical permittivity values, seismic data collection, and seismic interpretation. The data was input into GphyzCO2 to demonstrate a full implementation of the software capabilities. Part of the implementation investigated the limits of using geophysical methods to monitor CO{sub 2} injection sites. The results show that cross-hole EM numerical surveys are limited to under 100 meter borehole separation. Those results were utilized in executing numerical EM surveys that contain hypothetical CO{sub 2} injections. The outcome of the forward modeling shows that EM methods can detect the presence of CO{sub 2}.« less

Impact of CO 2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO 2 Leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna M.; Gregory, Kelvin B.; Lowry, Gregory V.

Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO 2) emissions to the atmosphere. During this process, CO 2 is injected as super critical carbon dioxide (SC-CO 2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO 2 in subsurface geologic formations could unintentionally lead to CO 2 leakage into overlying freshwater aquifers. Introduction of CO 2 into these subsurface environments will greatly increase the CO 2 concentration and will create CO 2 concentration gradients that drivemore » changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO 2 gradients will impact these communities. The overarching goal of this project is to understand how CO 2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO 2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO 2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO 2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO 2 injection/leakage plume where CO 2 concentrations are highest. At CO 2 exposures expected downgradient from the CO 2 plume, selected microorganisms emerged as dominant in the CO 2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site-dependent results suggest a limited ability to predict the emerging dominant species for other CO 2-exposed environments. This study improves the understanding of how a subsurface microbial community may respond to conditions expected from GCS and CO 2 leakage. This is the first step for understanding how a CO 2-altered microbial community may impact injectivity, permanence of stored CO 2, and subsurface water quality. Future work with microbial communities from new subsurface sites would increase the current understanding of this project. Additionally, incorporation of metagenomic methods would increase understanding of potential microbial processes that may be prevalent in CO 2 exposed environments.« less

Impact of CO 2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO 2 Leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna; Gregory, Kelvin B.; Lowry, Gregorgy V.

Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO 2) emissions to the atmosphere. During this process, CO 2 is injected as super critical carbon dioxide (SC-CO 2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO 2 in subsurface geologic formations could unintentionally lead to CO 2 leakage into overlying freshwater aquifers. Introduction of CO 2 into these subsurface environments will greatly increase the CO 22 concentration and will create CO 2 concentration gradients that drivemore » changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO 2 gradients will impact these communities. The overarching goal of this project is to understand how CO 2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO 2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO 2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO 2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO 2 injection/leakage plume where CO 2 concentrations are highest. At CO 2 exposures expected downgradient from the CO 2 plume, selected microorganisms emerged as dominant in the CO 2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site-dependent results suggest a limited ability to predict the emerging dominant species for other CO 2 exposed environments. This study improves the understanding of how a subsurface microbial community may respond to conditions expected from GCS and CO 2 leakage. This is the first step for understanding how a CO 2-altered microbial community may impact injectivity, permanence of stored CO 2, and subsurface water quality. Future work with microbial communities from new subsurface sites would increase the current understanding of this project. Additionally, incorporation of metagenomic methods would increase understanding of potential microbial processes that may be prevalent in CO 2 exposed environments.« less

Conceptual design of multi-source CCS pipeline transportation network for Polish energy sector

NASA Astrophysics Data System (ADS)

Isoli, Niccolo; Chaczykowski, Maciej

2017-11-01

The aim of this study was to identify an optimal CCS transport infrastructure for Polish energy sector in regards of selected European Commission Energy Roadmap 2050 scenario. The work covers identification of the offshore storage site location, CO2 pipeline network design and sizing for deployment at a national scale along with CAPEX analysis. It was conducted for the worst-case scenario, wherein the power plants operate under full-load conditions. The input data for the evaluation of CO2 flow rates (flue gas composition) were taken from the selected cogeneration plant with the maximum electric capacity of 620 MW and the results were extrapolated from these data given the power outputs of the remaining units. A graph search algorithm was employed to estimate pipeline infrastructure costs to transport 95 MT of CO2 annually, which amount to about 612.6 M€. Additional pipeline infrastructure costs will have to be incurred after 9 years of operation of the system due to limited storage site capacity. The results show that CAPEX estimates for CO2 pipeline infrastructure cannot be relied on natural gas infrastructure data, since both systems exhibit differences in pipe wall thickness that affects material cost.

Dopant-Site Determination in Y- and Sc-Doped (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ by Atom Location by Channeling Enhanced Microanalysis and the Role of Dopant Site on Secondary Phase Formation.

PubMed

Meffert, Matthias; Störmer, Heike; Gerthsen, Dagmar

2016-02-01

(Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) is a promising material with mixed ionic and electronic conductivity which is considered for oxygen separation membranes. Selective improvement of material properties, e.g. oxygen diffusivity or suppression of secondary phase formation, can be achieved by B-site doping. This study is concerned with the formation of Co-oxide precipitates in undoped BSCF at typical homogenization temperatures of 1,000°C, which act as undesirable nucleation sites for other secondary phases in the application-relevant temperature range. Y-doping successfully suppresses Co-oxide formation, whereas only minor improvements are achieved by Sc-doping. To understand the reason for the different behavior of Y and Sc, the lattice sites of dopant cations in BSCF were experimentally determined in this work. Energy-dispersive X-ray spectroscopy in a transmission electron microscope was applied to locate dopant sites exploiting the atom location by channeling enhanced microanalysis technique. It is shown that Sc exclusively occupies B-cation sites, whereas Y is detected on A- and B-cation sites in Y-doped BSCF, although solely B-site doping was intended. A model is presented for the suppression of Co-oxide formation in Y-doped BSCF based on Y double-site occupancy.

Therapeutic benefits of carbon dioxide (CO2) laser on single-site HPV lesions in the lower female genital tract

NASA Astrophysics Data System (ADS)

Urru, Giovanni; Moretti, Gianfranco

1998-01-01

Numerous studies have shown contradictory variable percentages of recurrent HPV lesions, after various therapies. The present study therefore evaluates the effectiveness of CO2 laser vaporization in the treatment of single-site HPV lesions of the lower female genital tract in order to confirm the conviction that physical therapy alone, in agreement with some findings reported in the literature, is capable of guaranteeing a high cure rate in selected patients. From January 1995 to June 1996, seventy- five female patients were treated with CO2 laser vaporization for single-site genital HPV lesions, some of which were associated with low-grade intra-epithelial neoplasia. The success rate after 12 months proved to be 97%. The pre-existing clinical symptoms disappeared in all the patients treated. No complication in the vaporization procedure was encountered.

Highly dispersed SiO x/Al 2O 3 catalysts illuminate the reactivity of isolated silanol sites

DOE PAGES

Mouat, Aidan R.; George, Cassandra; Kobayashi, Takeshi; ...

2015-09-23

The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiO x species on the alumina surface. These isolated (-AlO) 3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH 3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al 2O 3 surface, functionalizing the surface with “mild” Brønsted acid sites. As a result, for liquid-phase catalytic cyclohexanol dehydration, these SiO x sites exhibit up to 3.5-fold higher specific activity than the parent alumina withmore » identical selectivity.« less

Shape-Dependent Electrocatalytic Reduction of CO2 to CO on Triangular Silver Nanoplates.

PubMed

Liu, Subiao; Tao, Hongbiao; Zeng, Li; Liu, Qi; Xu, Zhenghe; Liu, Qingxia; Luo, Jing-Li

2017-02-15

Electrochemical reduction of CO 2 (CO 2 RR) provides great potential for intermittent renewable energy storage. This study demonstrates a predominant shape-dependent electrocatalytic reduction of CO 2 to CO on triangular silver nanoplates (Tri-Ag-NPs) in 0.1 M KHCO 3 . Compared with similarly sized Ag nanoparticles (SS-Ag-NPs) and bulk Ag, Tri-Ag-NPs exhibited an enhanced current density and significantly improved Faradaic efficiency (96.8%) and energy efficiency (61.7%), together with a considerable durability (7 days). Additionally, CO starts to be observed at an ultralow overpotential of 96 mV, further confirming the superiority of Tri-Ag-NPs as a catalyst for CO 2 RR toward CO formation. Density functional theory calculations reveal that the significantly enhanced electrocatalytic activity and selectivity at lowered overpotential originate from the shape-controlled structure. This not only provides the optimum edge-to-corner ratio but also dominates at the facet of Ag(100) where it requires lower energy to initiate the rate-determining step. This study demonstrates a promising approach to tune electrocatalytic activity and selectivity of metal catalysts for CO 2 RR by creating optimal facet and edge site through shape-control synthesis.

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby

Development of novel polymeric materials capable of efficient CO 2 capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO 2-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO 2 at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas systemmore » (20% CO 2, 80% N 2) similar to flue gas. CO 2 release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO 2 binding sites in the PBA functionalized polymer resulting in a two-step CO 2 release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO 2 capture.« less

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing

DOE PAGES

Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby; ...

2016-02-12

Development of novel polymeric materials capable of efficient CO 2 capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO 2-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO 2 at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas systemmore » (20% CO 2, 80% N 2) similar to flue gas. CO 2 release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO 2 binding sites in the PBA functionalized polymer resulting in a two-step CO 2 release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO 2 capture.« less

Integrating invasive grasses into carbon cycle projections: Cogongrass spread in southern pine forests

NASA Astrophysics Data System (ADS)

McCabe, T. D.; Flory, S. L.; Wiesner, S.; Dietze, M.

2017-12-01

Forested ecosystems are currently being disrupted by invasive species. One example is the invasive grass Imperata cylindrica (cogongrass), which is widespread in southeastern US pine forests. Pines forests dominate the forest cover of the southeast, and contribute to making the Southeast the United States' largest carbon sink. Cogongrass decreases the colonization of loblolly pine fine roots. If cogongrass continues to invade,this sink could be jeopardized. However, the effects of cogongrass invasion on carbon sequestration are largely unknown. We have projected the effects of elevated CO2 and changing climate on future cogongrass invasion. To test how pine stands are affected by cogongrass, cogongrass invasions were modeled using the Ecosystem Demography 2 (ED2) model, and parameterized using the Predictive Ecosystem Analyzer (PEcAn). ED2 takes into account local meteorological data, stand populations and succession, disturbance, and geochemical pools. PEcAn is a workflow that uses Bayesian sensitivity analyses and variance decomposition to quantify the uncertainty that each parameter contributes to overall model uncertainty. ED2 was run for four NEON and Ameriflux sites in the Southeast from the earliest available census of the site into 2010. These model results were compared to site measures to test for model accuracy and bias. To project the effect of elevated CO2 on cogongrass invasions, ED was run from 2006-2100 at four sites under four separate scenarios: 1) RPC4.5 CO2 and climate, 2) RPC4.5 climate only, with constant CO2 concentrations, 3) RPC4.5 Elevated CO2 only, with climate randomly selected from 2006-2026, 4) Present Day, made from randomly selected measures of CO2 and radiation from 2006-2026. Each scenario was run three times; once with cogongrass absent, once with a low cogongrass abundance, and once with a high cogongrass abundance. Model results suggest that many relevant parameters have high uncertainty due to lack of measurement. Further field work quantifying the carbon cycle, particularly belowground processes and respiration, could help constrain parameter uncertainty.

An Uncommon Carboxyl-Decorated Metal-Organic Framework with Selective Gas Adsorption and Catalytic Conversion of CO2.

PubMed

Li, Yong-Zhi; Wang, Hai-Hua; Yang, Hong-Yun; Hou, Lei; Wang, Yao-Yu; Zhu, Zhonghua

2018-01-19

A new three-dimensional (3D) framework, [Ni(btzip)(H 2 btzip)]⋅2 DMF⋅2 H 2 O (1) (H 2 btzip=4,6-bis(triazol-1-yl)isophthalic acid) as an acidic heterogeneous catalyst was constructed by the reaction of nickel wire and a triazolyl-carboxyl linker. Framework 1 possesses intersected 2D channels decorated by free COOH groups and uncoordinated triazolyl N atoms, leading to not only high CO 2 and C 2 H 6 adsorption capacity but also significant selective capture for CO 2 and C 2 H 6 over CH 4 and CO in 273-333 K. Moreover, 1 reveals chemical stability toward water. Grand Canonical Monte Carlo simulations confirmed the multiple CO 2 - and C 2 H 6 -philic sites. As a result of the presence of accessible Brønsted acidic COOH groups in the channels, the activated framework demonstrates highly efficient catalytic activity in the cycloaddition reaction of CO 2 with propylene oxide/4-chloromethyl-1,3-dioxolan-2-one/3-butoxy-1,2-epoxypropane into cyclic carbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Location and valence state of strontium cations on the framework of a carbon dioxide selective porous silicoaluminophosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Li; Rivera-Ramos, Milton E.; Hernández-Maldonado, Arturo J.

2014-05-28

A Sr{sup 2+}-SAPO-34 material that displays superior CO2 adsorption selectivity and capacity was characterized via XPS and UV-vis spectroscopy to elucidate the valence state of strontium cations and framework silicon environment. Most importantly, the location of the strontium has been estimated from a Rietveld refinement analysis of synchrotron diffraction data. The XPS analysis indicated that the apparent valence state of the strontium is less than 2, an indication of its interaction with the large anionic framework. Furthermore, UV-vis tests pointed to changes in the silicon environment, plausibly related to this valence state or framework faulting. For the refinement, the analysismore » found that strontium occupied two unique sites: a site Sr1 slightly displaced from six-membered rings and a site Sr2 positioned at the top or bottom of the eight-membered rings. The latter position favors the interaction of the alkaline earth metal with CO{sub 2}, probably resulting in an enhanced electric field-quadrupole moment interaction.« less

Selective oxidation of carbon monoxide in fuel processor gas

NASA Astrophysics Data System (ADS)

Manasilp, Akkarat

The trace amount of CO present in the hydrogen-rich stream coming from fuel reformers poisons the platinum anode electrode of proton exchange membrane (PEM) fuel cells and reduces the power output. Removal of low levels of CO present in the reformed gas must take place before the gas enters the fuel cell. The tolerable level of CO is around 10 ppm. We investigated the performance of single step sol-gel prepared Pt/alumina catalyst and Pt supported on sol gel made alumina. The effect of water vapor, carbon dioxide, CO and oxygen concentrations, temperature, and Pt loading on the activity and selectivity are presented. Our results showed that a 2%Pt/alumina sol-gel catalyst can selectively oxide CO down to a few ppm with constant selectivity and high space velocity. Water vapor in the feed increases the activity of catalysts dramatically and in the absence of water vapor, CO2 in the feed stream decreases the activity of the catalysts significantly. We also found that the presence of potassium as an electron donor did not improve the performance of Pt/alumina catalyst to the selective CO oxidation. For Pt supported on sol gel made alumina, we found that the combination of CO2 and H2O in the gas feed has a strong effect on selective CO oxidation over Pt/Al2O3. It could be a positive or negative effect depending upon Pt loading in the catalyst. With high Pt loading, the CO2 effect tends to dominate the H2O effect resulting in the decrease in CO conversion. Moreover, the presence of CeO2 as an oxygen storage compound promotes the performance of Pt supported on alumina at low temperature ˜90°C when Pt loading was 5%. Amongst the examined catalysts, the 5%Pt/15%CeO2/Al 2O3 catalyst showed the highest selectivity, with high CO conversion at a low temperature ˜90°C. The beneficial effect of the addition of CeO2 is most likely due to spillover of O2 from CeO2 to Pt at the Pt sites at the interface of Pt and CeO 2.

Binding site exploration of CCR5 using in silico methodologies: a 3D-QSAR approach.

PubMed

Gadhe, Changdev G; Kothandan, Gugan; Cho, Seung Joo

2013-01-01

Chemokine receptor 5 (CCR5) is an important receptor used by human immunodeficiency virus type 1 (HIV-1) to gain viral entry into host cell. In this study, we used a combined approach of comparative modeling, molecular docking, and three dimensional quantitative structure activity relationship (3D-QSAR) analyses to elucidate detailed interaction of CCR5 with their inhibitors. Docking study of the most potent inhibitor from a series of compounds was done to derive the bioactive conformation. Parameters such as random selection, rational selection, different charges and grid spacing were utilized in the model development to check their performance on the model predictivity. Final comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) models were chosen based on the rational selection method, Gasteiger-Hückel charges and a grid spacing of 0.5 Å. Rational model for CoMFA (q(2) = 0.722, r(2) = 0.884, Q(2) = 0.669) and CoMSIA (q(2) = 0.712, r(2) = 0.825, Q(2) = 0.522) was obtained with good statistics. Mapping of contour maps onto CCR5 interface led us to better understand of the ligand-protein interaction. Docking analysis revealed that the Glu283 is crucial for interaction. Two new amino acid residues, Tyr89 and Thr167 were identified as important in ligand-protein interaction. No site directed mutagenesis studies on these residues have been reported.

Design Considerations for Financing a National Trust to Advance the Deployment of Geologic CO2 Storage and Motivate Best Practices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dooley, James J.; Trabucchi, Chiara; Patton , Lindene

2010-03-01

This paper explores how the flawed, widely held public policy view of an ever growing risk associated with long-term carbon dioxide (CO2) storage profoundly influences the public policy dialogue about how to best address the long term risk profile for geologic storage. In order to accomplish this, the authors present evidence from the rapidly emerging science and engineering of CO2 storage which demonstrates that, with proper site characterization and sound operating practices, retention of stored CO2 will increase with time thus invalidating the premise of an ever growing risk. The authors focus on key issues of fit, interplay, and scalabilitymore » associated with a trust fund funded by a hypothetical $1/tonCO2 tipping fee for each ton of CO2 stored in the United States under WRE450 and WRE550 climate policies. The authors conclude there is no intrinsic value in creating a trust fund predicated solely on collecting a fixed fee that is not mapped to site-specific risk profiles. If left to grow unchecked, a trust fund that is predicated on a constant stream of annual payments unrelated to the site’s risk profile could result in the accumulation of hundreds of billions to more than a trillion dollars in real terms contributing to significant opportunity cost of capital. Further, rather than mitigating the financial consequences of long-term CCS risks, this analysis suggests a blanket $1/tonCO2 tipping fee may increase the probability and frequency of long-term risk by eliminating financial incentives for sound operating behavior and site selection criteria – contribute to moral hazard. At a minimum, effective use of a trust fund requires: (1) strong oversight regarding site selection and fund management, and (2) a clear process by which the fund is periodically valued and funds collected are mapped to the risk profile of the pool of covered CCS sites. Without appropriate checks and balances, there is no a priori reason to believe that the amount of funds held in trust will map to the actual amount of funds needed to address long-term care expenses and delimited compensatory damages. For this reason, the authors conclude that the financing of a trust fund or other risk management instrument should be based on a site delimited estimate of future expected financial consequences rather than on the random adoption of a fixed funding stream, e.g., a blanket $1/ton , because it ‘sounds’ reasonable.« less

Biosphere/atmosphere CO2 exchange in tundra ecosystems - Community characteristics and relationships with multispectral surface reflectance

NASA Technical Reports Server (NTRS)

Whiting, Gary J.; Bartlett, David S.; Fan, Song-Miao; Bakwin, Peter S.; Wofsy, Steven C.

1992-01-01

CO2 exchange rates were measured at selected tundra sites near Bethel, Alaska using portable, climate-controlled, instrumented enclosures. The empirically modeled exchange rate for a representative area of vegetated tundra was 1.2 +/- 1.2 g/sq m/d, compared to a tower-measured exchange over the same time period of 1.1 +.0- 1.2 g/sq m/d. Net exchange in response to varying light levels was compared to wet meadow and dry upland tundra, and to the net exchange measured by the micrometeoroidal tower technique. The multispectral reflectance properties of the sites were measured and related to exchange rates in order to provide a quantitative foundation for the use of satellite remote sensing to monitor biosphere/atmosphere CO2 exchange in the tundra biome.

The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts

DOE PAGES

Yang, Nuoya; Liu, Xinyan; Asundi, Arun S.; ...

2017-10-23

Alkali metal oxides commonly exist as impurities or promoters in syngas conversion catalysts and can significantly influence the activity and selectivity towards higher oxygenate products. In this study, we investigate the effects of sodium oxide on silica-supported Rh catalysts by experimentally introducing different amounts of sodium and monitoring the change in reactivity and CO adsorption behavior. The experimental results combined with density functional theory (DFT) calculations show that sodium selectively blocks step/defect sites on Rh surfaces, leading to reduced activity but higher C 2 oxygenate selectivity. DFT calculations also suggest that sodium present on Rh terrace sites can facilitate COmore » dissociation, potentially increasing C 2 oxygenate production. The overall activity and selectivity toward various products can be changed significantly based on the degree of site blocking by the added sodium.« less

The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Nuoya; Liu, Xinyan; Asundi, Arun S.

Alkali metal oxides commonly exist as impurities or promoters in syngas conversion catalysts and can significantly influence the activity and selectivity towards higher oxygenate products. In this study, we investigate the effects of sodium oxide on silica-supported Rh catalysts by experimentally introducing different amounts of sodium and monitoring the change in reactivity and CO adsorption behavior. The experimental results combined with density functional theory (DFT) calculations show that sodium selectively blocks step/defect sites on Rh surfaces, leading to reduced activity but higher C 2 oxygenate selectivity. DFT calculations also suggest that sodium present on Rh terrace sites can facilitate COmore » dissociation, potentially increasing C 2 oxygenate production. The overall activity and selectivity toward various products can be changed significantly based on the degree of site blocking by the added sodium.« less

Adaptive selection of diurnal minimum variation: a statistical strategy to obtain representative atmospheric CO2 data and its application to European elevated mountain stations

NASA Astrophysics Data System (ADS)

Yuan, Ye; Ries, Ludwig; Petermeier, Hannes; Steinbacher, Martin; Gómez-Peláez, Angel J.; Leuenberger, Markus C.; Schumacher, Marcus; Trickl, Thomas; Couret, Cedric; Meinhardt, Frank; Menzel, Annette

2018-03-01

Critical data selection is essential for determining representative baseline levels of atmospheric trace gases even at remote measurement sites. Different data selection techniques have been used around the world, which could potentially lead to reduced compatibility when comparing data from different stations. This paper presents a novel statistical data selection method named adaptive diurnal minimum variation selection (ADVS) based on CO2 diurnal patterns typically occurring at elevated mountain stations. Its capability and applicability were studied on records of atmospheric CO2 observations at six Global Atmosphere Watch stations in Europe, namely, Zugspitze-Schneefernerhaus (Germany), Sonnblick (Austria), Jungfraujoch (Switzerland), Izaña (Spain), Schauinsland (Germany), and Hohenpeissenberg (Germany). Three other frequently applied statistical data selection methods were included for comparison. Among the studied methods, our ADVS method resulted in a lower fraction of data selected as a baseline with lower maxima during winter and higher minima during summer in the selected data. The measured time series were analyzed for long-term trends and seasonality by a seasonal-trend decomposition technique. In contrast to unselected data, mean annual growth rates of all selected datasets were not significantly different among the sites, except for the data recorded at Schauinsland. However, clear differences were found in the annual amplitudes as well as the seasonal time structure. Based on a pairwise analysis of correlations between stations on the seasonal-trend decomposed components by statistical data selection, we conclude that the baseline identified by the ADVS method is a better representation of lower free tropospheric (LFT) conditions than baselines identified by the other methods.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Experimental investigations and geochemical modelling of site-specific fluid-fluid and fluid-rock interactions in underground storage of CO2/H2/CH4 mixtures: the H2STORE project

NASA Astrophysics Data System (ADS)

De Lucia, Marco; Pilz, Peter

2015-04-01

Underground gas storage is increasingly regarded as a technically viable option for meeting the energy demand and environmental targets of many industrialized countries. Besides the long-term CO2 sequestration, energy can be chemically stored in form of CO2/CH4/H2 mixtures, for example resulting from excess wind energy. A precise estimation of the impact of such gas mixtures on the mineralogical, geochemical and petrophysical properties of specific reservoirs and caprocks is crucial for site selection and optimization of storage depth. Underground gas storage is increasingly regarded as a technically viable option for meeting environmental targets and the energy demand through storage in form of H2 or CH4, i.e. resulting from excess wind energy. Gas storage in salt caverns is nowadays a mature technology; in regions where favorable geologic structures such as salt diapires are not available, however, gas storage can only be implemented in porous media such as depleted gas and oil reservoirs or suitable saline aquifers. In such settings, a significant amount of in-situ gas components such as CO2, CH4 (and N2) will always be present, making the CO2/CH4/H2 system of particular interest. A precise estimation of the impact of their gas mixtures on the mineralogical, geochemical and petrophysical properties of specific reservoirs and caprocks is therefore crucial for site selection and optimization of storage depth. In the framework of the collaborative research project H2STORE, the feasibility of industrial-scale gas storage in porous media in several potential siliciclastic depleted gas and oil reservoirs or suitable saline aquifers is being investigated by means of experiments and modelling on actual core materials from the evaluated sites. Among them are the Altmark depleted gas reservoir in Saxony-Anhalt and the Ketzin pilot site for CO2 storage in Brandenburg (Germany). Further sites are located in the Molasse basin in South Germany and Austria. In particular, two work packages hosted at the German Research Centre for Geosciences (GFZ) focus on the fluid-fluid and fluid-rock interactions triggered by CO2, H2 and their mixtures. Laboratory experiments expose core samples to hydrogen and CO2/hydrogen mixtures under site-specific conditions (temperatures up to 200 °C and pressure up to 300 bar). The resulting qualitative and, whereas possible, quantitative data are expected to ameliorate the precision of predictive geochemical and reactive transport modelling, which is also performed within the project. The combination of experiments, chemical and mineralogical analyses and models is needed to improve the knowledge about: (1) solubility model and mixing rule for multicomponent gas mixtures in high saline formation fluids: no data are namely available in literature for H2-charged gas mixtures in the conditions expected in the potential sites; (2) chemical reactivity of different mineral assemblages and formation fluids in a broad spectrum of P-T conditions and composition of the stored gas mixtures; (3) thermodynamics and kinetics of relevant reactions involving mineral dissolution or precipitation. The resulting amelioration of site characterization and the overall enhancement in understanding the potential processes will benefit the operational reliability, the ecological tolerance, and the economic efficiency of future energy storing plants, crucial aspects for public acceptance and for industrial investors.

RubisCO selection using the vigorously aerobic and metabolically versatile bacterium Ralstonia eutropha.

PubMed

Satagopan, Sriram; Tabita, F Robert

2016-08-01

Recapturing atmospheric CO2 is key to reducing global warming and increasing biological carbon availability. Ralstonia eutropha is a biotechnologically useful aerobic bacterium that uses the Calvin-Benson-Bassham (CBB) cycle and the enzyme ribulose 1,5-bisphosphate carboxylase/oxygenase (RubisCO) for CO2 utilization, suggesting that it may be a useful host to bioselect RubisCO molecules with improved CO2 -capture capabilities. A host strain of R. eutropha was constructed for this purpose after deleting endogenous genes encoding two related RubisCOs. This strain could be complemented for CO2 -dependent growth by introducing native or heterologous RubisCO genes. Mutagenesis and suppressor selection identified amino acid substitutions in a hydrophobic region that specifically influences RubisCO's interaction with its substrates, particularly O2 , which competes with CO2 at the active site. Unlike most RubisCOs, the R. eutropha enzyme has evolved to retain optimal CO2 -fixation rates in a fast-growing host, despite the presence of high levels of competing O2 . Yet its structure-function properties resemble those of several commonly found RubisCOs, including the higher plant enzymes, allowing strategies to engineer analogous enzymes. Because R. eutropha can be cultured rapidly under harsh environmental conditions (e.g., with toxic industrial flue gas), in the presence of near saturation levels of oxygen, artificial selection and directed evolution studies in this organism could potentially impact efforts toward improving RubisCO-dependent biological CO2 utilization in aerobic environments. d-ribulose 1,5-bisphosphate carboxylase/oxygenase, EC 4.1.1.39; phosphoribulokinase, EC 2.7.1.19. © 2016 Federation of European Biochemical Societies.

Measurements of CO2 Mole Fractionand δ13C in Archived Air Samples from Cape Meares, Oregon (USA) 1977 - 1998

NASA Astrophysics Data System (ADS)

Clark, O.; Rice, A. L.

2017-12-01

Carbon dioxide (CO2) is the most abundant, anthropogenically forced greenhouse gas (GHG) in the global atmosphere. Emissions of CO2 account for approximately 75% of the world's total GHG emissions. Atmospheric concentrations of CO2 are higher now than they've been at any other time in the past 800,000 years. Currently, the global mean concentration exceeds 400 ppm. Today, global networks regularly monitor CO2 concentrations and isotopic composition (δ13C and δ18O). However, past data is sparse. Over 200 ambient air samples from Cape Meares, Oregon (45.5°N, 124.0°W), a coastal site in Western United States, were obtained by researchers at Oregon Institute of Science and Technology (OGI, now Oregon Health & Science University), between the years of 1977 and 1998 as part of a global monitoring program of six different sites in the polar, middle, and tropical latitudes of the Northern and Southern Hemispheres. Air liquefaction was used to compress approximately 1000L of air (STP) to 30bar, into 33L electropolished (SUMMA) stainless steel canisters. Select archived air samples from the original network are maintained at Portland State University (PSU) Department of Physics. These archived samples are a valuable look at changing atmospheric concentrations of CO2 and δ13C, which can contribute to a better understanding of changes in sources during this time. CO2 concentrations and δ13C of CO2 were measured at PSU, with a Picarro Cavity Ringdown Spectrometer, model G1101-i analytical system. This study presents the analytical methods used, calibration techniques, precision, and reproducibility. Measurements of select samples from the archive show rising CO2 concentrations and falling δ13C over the 1977 to 1998 period, compatible with previous observations and rising anthropogenic sources of CO2. The resulting data set was statistically analyzed in MATLAB. Results of preliminary seasonal and secular trends from the archive samples are presented.

Polyacrylonitrile-Derived Sponge-Like Micro/Macroporous Carbon for Selective CO2 Separation.

PubMed

Guo, Li-Ping; Hu, Qing-Tao; Zhang, Peng; Li, Wen-Cui; Lu, An-Hui

2018-06-12

CO 2 capture under a dynamical flow situation requires adsorbents possessing balanced proportion of macropores as diffusion path and micropores as adsorption reservoir. However, the construction of interconnected micro-/macropores structure coupled with abundant nitrogen species into one carbon skeleton remains a challenge. Here, we report a new approach to prepare sponge-like carbon with a well-developed micro-/macroporous structure and enriched nitrogen species through aqueous phase polymerization of acrylonitrile in the presence of graphene oxide. The tension stress caused by the uniform thermal shrinkage of polyacrylonitrile during the pyrolysis together with the favorable flexibility of graphene oxide sheets are responsible for the formation of the sponge-like morphology. The synergistic effect of micro-/macroporous framework and rich CO 2 -philic site enables such carbon to decrease resistance to mass transfer and show high CO 2 dynamic selectivity over N 2 (454) and CH 4 (11), as well as good CO 2 capacity at 298 K under low CO 2 partial pressure (0.17 bar, a typical CO 2 partial pressure in flue gas). The above attributes make this porous carbon a promising candidate for CO 2 capture from flue gas, methane sources and other relevant applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Investigations of CO2 and CH4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material

PubMed Central

2015-01-01

Grand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal–organic material (MOM) consisting of a 7-fold interpenetrated net of Co2+ ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels—this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM’s high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity. PMID:24835550

Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO 2

DOE PAGES

Siahrostami, Samira; Jiang, Kun; Karamad, Mohammadreza; ...

2017-10-10

Here, despite numerous experimental efforts that have been dedicated to studying carbon-based materials for electrochemical reduction of CO 2, a rationalization of the associated trends in the intrinsic activity of different active motifs has so far been elusive. In the present work, we employ density functional theory calculations to examine a variety of different active sites in N-doped graphene to give a comprehensive outline of the trends in activity. We find that adsorption energies of COOH* and CO* do not follow the linear scaling relationships observed for the pure transition metals, and this unique scaling is rationalized through differences inmore » electronic structure between transition metals and defected graphene. This finding rationalizes most of the experimental observations on the carbon-based materials which present promising catalysts for the two-electron reduction of CO 2 to CO. With this simple thermodynamic analysis, we identify several active sites that are expected to exhibit a comparable or even better activity to the state-of-the-art gold catalyst, and several configurations are suggested to be selective for CO 2RR over HER.« less

Ultrahigh vacuum and high-pressure coadsorption of CO and H2 on Pd(111): A combined SFG, TDS, and LEED study

NASA Astrophysics Data System (ADS)

Morkel, Matthias; Rupprechter, Günther; Freund, Hans-Joachim

2003-11-01

Sum frequency generation (SFG) vibrational spectroscopy was carried out in conjunction with thermal desorption spectroscopy, low-energy electron diffraction, and Auger electron spectroscopy to examine the coadsorption of CO and H2 on Pd(111). Sequential dosing as well as various CO/H2 mixtures was utilized to study intermolecular interactions between CO and H2. Preadsorbed CO effectively prevented the dissociative adsorption of hydrogen for CO coverages ⩾0.33 ML. While preadsorbed hydrogen was able to hinder CO adsorption at low temperature (100 K), hydrogen was replaced from the surface by CO at 150 K. When 1:1 mixtures of CO/H2 were used at 100 K, hydrogen selectively hindered CO adsorption on on-top sites, while above ˜125 K no blocking of CO adsorption was observed. The observations are explained in terms of mutual site blocking, of a CO-H phase separation, and of a CO-assisted hydrogen dissolution in the Pd bulk. The temperature-dependent site blocking effect of hydrogen is attributed to the ability (inability) of surface hydrogen to diffuse into the Pd bulk above (below) ˜125 K. Nonlinear optical SFG spectroscopy allowed us to study these effects not only in ultrahigh vacuum but also in a high-pressure environment. Using an SFG-compatible ultrahigh vacuum-high-pressure cell, spectra of 1:10 CO/H2 mixtures were acquired up to 55 mbar and 550 K, with simultaneous gas chromatographic and mass spectrometric gas phase analysis. Under reaction conditions, CO coverages ⩾0.5 ML were observed which strongly limit H2 adsorption and thus may be partly responsible for the low CO hydrogenation rate. The high-pressure and high-temperature SFG spectra also showed indications of a reversible surface roughening or a highly dynamic (not perfectly ordered) CO adsorbate phase. Implications of the observed adsorbate structures on catalytic CO hydrogenation on supported Pd nanoparticles are discussed.

Twin defects engineered Pd cocatalyst on C3N4 nanosheets for enhanced photocatalytic performance in CO2 reduction reaction

NASA Astrophysics Data System (ADS)

Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song

2017-12-01

Photocatalytic conversion of CO2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C3N4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO2 to CO and CH4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.

Twin defects engineered Pd cocatalyst on C3N4 nanosheets for enhanced photocatalytic performance in CO2 reduction reaction.

PubMed

Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song

2017-12-01

Photocatalytic conversion of CO 2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO 2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO 2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C 3 N 4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO 2 to CO and CH 4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO 2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO 2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.

High-Density Nanosharp Microstructures Enable Efficient CO2 Electroreduction.

PubMed

Saberi Safaei, Tina; Mepham, Adam; Zheng, Xueli; Pang, Yuanjie; Dinh, Cao-Thang; Liu, Min; Sinton, David; Kelley, Shana O; Sargent, Edward H

2016-11-09

Conversion of CO 2 to CO powered by renewable electricity not only reduces CO 2 pollution but also is a means to store renewable energy via chemical production of fuels from CO. However, the kinetics of this reaction are slow due its large energetic barrier. We have recently reported CO 2 reduction that is considerably enhanced via local electric field concentration at the tips of sharp gold nanostructures. The high local electric field enhances CO 2 concentration at the catalytic active sites, lowering the activation barrier. Here we engineer the nucleation and growth of next-generation Au nanostructures. The electroplating overpotential was manipulated to generate an appreciably increased density of honed nanoneedles. Using this approach, we report the first application of sequential electrodeposition to increase the density of sharp tips in CO 2 electroreduction. Selective regions of the primary nanoneedles are passivated using a thiol SAM (self-assembled monolayer), and then growth is concentrated atop the uncovered high-energy planes, providing new nucleation sites that ultimately lead to an increase in the density of the nanosharp structures. The two-step process leads to a new record in CO 2 to CO reduction, with a geometric current density of 38 mA/cm 2 at -0.4 V (vs reversible hydrogen electrode), and a 15-fold improvement over the best prior reports of electrochemical surface area (ECSA) normalized current density.

Influence of * OH adsorbates on the potentiodynamics of the CO 2 generation during the electro-oxidation of ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Guangxing; Namin, Lida M.; Aaron Deskins, N.

Direct ethanol fuel cells (DEFCs) are a promising technology for the generation of electricity via the direct conversion of ethanol into CO2, showing higher thermodynamic efficiency and volumetric energy density than hydrogen fuel cells. However, implementation of DEFCs is hampered by the low CO2 selectivity during the ethanol oxidation reaction (EOR). Comprehensive understanding of the electro-kinetics and reaction pathways of CO2 generation via CC bond-breaking is not only a fundamental question for electro-catalysis, but also a key technological challenge since practical implementation of DEFC technology is contingent on its ability to selectively oxidize ethanol into CO2 to achieve exceptional energymore » density through 12-electron transfer reaction. Here, we present comprehensive in situ potentiodynamics studies of CO2 generation during the EOR on Pt, Pt/SnO2 and Pt/Rh/SnO2 catalysts using a house-made electrochemical cell equipped with a CO2 microelectrode. Highly sensitive CO2 measurements enable the real time detection of the partial pressure of CO2 during linear sweep voltammetry measurements, through which electro-kinetics details of CO2 generation can be obtained. In situ CO2 measurements provide the mechanistic understanding of potentiodynamics of the EOR, particularly the influence of *OH adsorbates on CO2 generation rate and selectivity. Density functional theory (DFT) simulations of Pt, Pt/SnO2, and Pt/Rh/SnO2 surfaces clarify reaction details over these catalysts. Our results show that at low potentials, inadequate *OH adsorbates impair the removal of reaction intermediates, and thus Pt/Rh/SnO2 exhibited the best performance toward CO2 generation, while at high potentials, Rh sites were overwhelmingly occupied (poisoned) by *OH adsorbates, and thus Pt/SnO2 exhibited the best performance toward CO2 generation.« less

Influence of *OH adsorbates on the potentiodynamics of the CO 2 generation during the electro-oxidation of ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Guangxing; Namin, Lida M.; Aaron Deskins, N.

Direct ethanol fuel cells (DEFCs) are a promising technology for the generation of electricity via the direct conversion of ethanol into CO 2, showing higher thermodynamic efficiency and volumetric energy density than hydrogen fuel cells. However, implementation of DEFCs is hampered by the low CO 2 selectivity during the ethanol oxidation reaction (EOR). Comprehensive understanding of the electro-kinetics and reaction pathways of CO 2 generation via CC bond-breaking is not only a fundamental question for electro-catalysis, but also a key technological challenge since practical implementation of DEFC technology is contingent on its ability to selectively oxidize ethanol into CO 2more » to achieve exceptional energy density through 12-electron transfer reaction. Here, we present comprehensive in situ potentiodynamics studies of CO 2 generation during the EOR on Pt, Pt/SnO 2 and Pt/Rh/SnO 2 catalysts using a house-made electrochemical cell equipped with a CO 2 microelectrode. Highly sensitive CO 2 measurements enable the real time detection of the partial pressure of CO 2 during linear sweep voltammetry measurements, through which electro-kinetics details of CO 2 generation can be obtained. In situ CO 2 measurements provide the mechanistic understanding of potentiodynamics of the EOR, particularly the influence of *OH adsorbates on CO 2 generation rate and selectivity. Density functional theory (DFT) simulations of Pt, Pt/SnO 2, and Pt/Rh/SnO 2 surfaces clarify reaction details over these catalysts. Our results show that at low potentials, inadequate *OH adsorbates impair the removal of reaction intermediates, and thus Pt/Rh/SnO 2 exhibited the best performance toward CO 2 generation, while at high potentials, Rh sites were overwhelmingly occupied (poisoned) by *OH adsorbates, and thus Pt/SnO 2 exhibited the best performance toward CO 2 generation.« less

Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nie, Lei; Mei, Donghai; Xiong, Haifeng

While single-atom catalysts can provide high catalytic activity and selectivity, application in industrial catalysts demands long term performance and the ability to regenerate the catalysts. We have investigated the factors that lead to improved catalytic activity of a Pt/CeO2 catalyst for low temperature CO oxidation. Single-atom Pt/CeO2 becomes active for CO oxidation under lean condition only at elevated temperatures, because CO is strongly bound to ionic Pt sites. Reducing the catalyst, even under mild conditions, leads to onset of CO oxidation activity even at room temperature. This high activity state involves the transformation of mononuclear Pt species to sub-nanometer sizedmore » Pt particles. Under oxidizing conditions, the Pt can be restored to its stable, single-atom state. The key to facile regeneration is the ability to create mobile Pt species and suitable trapping sites on the support, making this a prototypical catalyst system for industrial application of single-atom catalysis.« less

Two Analogous Polyhedron-Based MOFs with High Density of Lewis Basic Sites and Open Metal Sites: Significant CO2 Capture and Gas Selectivity Performance.

PubMed

Liu, Bing; Yao, Shuo; Liu, Xinyao; Li, Xu; Krishna, Rajamani; Li, Guanghua; Huo, Qisheng; Liu, Yunling

2017-09-27

By means of modulating the axial ligand and adopting supermolecular building blocks (SBBs) strategy, two polyhedron-based metal-organic frameworks (PMOFs) have been successfully synthesized [Cu 6 (C 17 O 9 N 2 H 8 ) 3 (C 6 H 12 N 2 )(H 2 O) 2 (DMF) 2 ]·3DMF·8H 2 O (JLU-Liu46) and [Cu 6 (C 17 O 9 N 2 H 8 ) 3 (C 4 H 4 N 2 )(H 2 O) 2 (DMF) 2 ]·3DMF·8H 2 O (JLU-Liu47), which possess a high density of Lewis basic sites (LBSs) and open metal sites (OMSs). Since the size of axial ligand in JLU-Liu47 is smaller than that in JLU-Liu46, JLU-Liu47 shows larger pore volume and higher BET surface area. Then, the adsorption ability of JLU-Liu47 for some small gases is better than JLU-Liu46. It is worthwhile to mention that both of the two compounds exhibit outstanding adsorption capability for CO 2 ascribed to the introducing of urea groups. In addition, the theoretical ideal adsorbed solution theory (IAST) calculation and transient breakthrough simulation indicate that JLU-Liu46 and JLU-Liu47 should be potential materials for gas storage and separation, particularly for CO 2 /N 2 , CO 2 /CH 4 , and C 3 H 8 /CH 4 separation.

Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

NASA Astrophysics Data System (ADS)

Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

2018-03-01

The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.

Final Technical Report. Reactivity of Iron-Bearing Minerals and CO 2 Sequestration and Surface Chemistry of Pyrite. An Interdisciplinary Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strongin, Daniel

2014-12-31

Over the course of the scientific program, two areas of research were pursued: reactions of iron oxides with supercritical CO 2 and sulfide and surface reactivity of pyrite. The latter area of interest was to understand the chemistry that results when supercritical CO 2 (scCO 2 ) with H 2 S and/or SO 2 in deep saline formations (DFS) contacts iron bearing minerals. Understanding the complexities the sulfur co-injectants introduce is a critical step in developing CO 2 sequestration as a climate-mitigating strategy. The research strategy was to understand macroscopic observations of this chemistry with anmore » atomic/molecular level view using surface analytical techniques. Research showed that the exposure of iron (oxyhdr)oxides (which included ferrihydrite, goethite, and hematite) to scCO 2 in the presence of sulfide led to reactions that formed siderite (FeCO 3). The results have important implications for the sequestration of CO 2 via carbonation reactions in the Earth’s subsurface. An earlier area of focus in the project was to understand pyrite oxidation in microscopic detail. This understanding was used to understand macroscopic observations of pyrite reactivity. Results obtained from this research led to a better understanding how pyrite reacts in a range of chemical environments. Geochemical and modern surface science techniques were used to understand the chemistry of pyrite in important environmental conditions. The program relied on a strong integration the results of these techniques to provide a fundamental understanding to the macroscopic chemistry exhibited by pyrite in the environment. Major achievements during these studies included developing an understanding of the surface sites on pyrite that controlled its reactivity under oxidizing conditions. In particular sulfur anion vacancies and/or ferric sites were sites of reactivity. Studies also showed that the adsorption of phospholipid on the surface to selectively suppress the reactivity of these sites could of potential importance for suppressing acid mine drainage in the environment (a problem common to coal-mining sites). Biotic studies showed that microbial activity that promotes the oxidation of pyrite to produce AMD could also be suppressed by the adsorption of phospholipid.« less

Deep aquifer prokaryotic community responses to CO2 geosequestration

NASA Astrophysics Data System (ADS)

Mu, A.; Moreau, J. W.

2015-12-01

Little is known about potential microbial responses to supercritical CO2 (scCO2) injection into deep subsurface aquifers, a currently experimental means for mitigating atmospheric CO2 pollution being trialed at several locations around the world. One such site is the Paaratte Formation of the Otway Basin (~1400 m below surface; 60°C; 2010 psi), Australia. Microbial responses to scCO2 are important to understand as species selection may result in changes to carbon and electron flow. A key aim is to determine if biofilm may form in aquifer pore spaces and reduce aquifer permeability and storage. This study aimed to determine in situ, using 16S rRNA gene, and functional metagenomic analyses, how the microbial community in the Otway Basin geosequestration site responded to experimental injection of 150 tons of scCO2. We demonstrate an in situ sampling approach for detecting deep subsurface microbial community changes associated with geosequestration. First-order level analyses revealed a distinct shift in microbial community structure following the scCO2 injection event, with proliferation of genera Comamonas and Sphingobium. Similarly, functional profiling of the formation revealed a marked increase in biofilm-associated genes (encoding for poly-β-1,6-N-acetyl-D-glucosamine). Global analysis of the functional gene profile highlights that scCO2 injection potentially degraded the metabolism of CH4 and lipids. A significant decline in carboxydotrophic gene abundance (cooS) and an anaerobic carboxydotroph OTU (Carboxydocella), was observed in post-injection samples. The potential impacts on the flow networks of carbon and electrons to heterotrophs are discussed. Our findings yield insights for other subsurface systems, such as hydrocarbon-rich reservoirs and high-CO2 natural analogue sites.

How can mountaintop CO 2 observations be used to constrain regional carbon fluxes?

DOE PAGES

Lin, John C.; Mallia, Derek V.; Wu, Dien; ...

2017-05-03

Despite the need for researchers to understand terrestrial biospheric carbon fluxes to account for carbon cycle feedbacks and predict future CO 2 concentrations, knowledge of these fluxes at the regional scale remains poor. This is particularly true in mountainous areas, where complex meteorology and lack of observations lead to large uncertainties in carbon fluxes. Yet mountainous regions are often where significant forest cover and biomass are found – i.e., areas that have the potential to serve as carbon sinks. As CO 2 observations are carried out in mountainous areas, it is imperative that they are properly interpreted to yield informationmore » about carbon fluxes. In this paper, we present CO 2 observations at three sites in the mountains of the western US, along with atmospheric simulations that attempt to extract information about biospheric carbon fluxes from the CO 2 observations, with emphasis on the observed and simulated diurnal cycles of CO 2. We show that atmospheric models can systematically simulate the wrong diurnal cycle and significantly misinterpret the CO 2 observations, due to erroneous atmospheric flows as a result of terrain that is misrepresented in the model. This problem depends on the selected vertical level in the model and is exacerbated as the spatial resolution is degraded, and our results indicate that a fine grid spacing of ~4 km or less may be needed to simulate a realistic diurnal cycle of CO 2 for sites on top of the steep mountains examined here in the American Rockies. In conclusion, in the absence of higher resolution models, we recommend coarse-scale models to focus on assimilating afternoon CO 2 observations on mountaintop sites over the continent to avoid misrepresentations of nocturnal transport and influence.« less

How can mountaintop CO2 observations be used to constrain regional carbon fluxes?

NASA Astrophysics Data System (ADS)

Lin, John C.; Mallia, Derek V.; Wu, Dien; Stephens, Britton B.

2017-05-01

Despite the need for researchers to understand terrestrial biospheric carbon fluxes to account for carbon cycle feedbacks and predict future CO2 concentrations, knowledge of these fluxes at the regional scale remains poor. This is particularly true in mountainous areas, where complex meteorology and lack of observations lead to large uncertainties in carbon fluxes. Yet mountainous regions are often where significant forest cover and biomass are found - i.e., areas that have the potential to serve as carbon sinks. As CO2 observations are carried out in mountainous areas, it is imperative that they are properly interpreted to yield information about carbon fluxes. In this paper, we present CO2 observations at three sites in the mountains of the western US, along with atmospheric simulations that attempt to extract information about biospheric carbon fluxes from the CO2 observations, with emphasis on the observed and simulated diurnal cycles of CO2. We show that atmospheric models can systematically simulate the wrong diurnal cycle and significantly misinterpret the CO2 observations, due to erroneous atmospheric flows as a result of terrain that is misrepresented in the model. This problem depends on the selected vertical level in the model and is exacerbated as the spatial resolution is degraded, and our results indicate that a fine grid spacing of ˜ 4 km or less may be needed to simulate a realistic diurnal cycle of CO2 for sites on top of the steep mountains examined here in the American Rockies. In the absence of higher resolution models, we recommend coarse-scale models to focus on assimilating afternoon CO2 observations on mountaintop sites over the continent to avoid misrepresentations of nocturnal transport and influence.

Water oxidation by size selected Co 27 clusters supported on Fe 2O 3

DOE PAGES

Pellin, Michael J.; Riha, Shannon C.; Tyo, Eric C.; ...

2016-09-22

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27) deposited on hematite (Fe 2O 3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination atmore » the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27/Fe 2O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.« less

Applicability of aquifer impact models to support decisions at CO 2 sequestration sites

DOE PAGES

Keating, Elizabeth; Bacon, Diana; Carroll, Susan; ...

2016-07-25

The National Risk Assessment Partnership has developed a suite of tools to assess and manage risk at CO 2 sequestration sites. This capability includes polynomial or look-up table based reduced-order models (ROMs) that predict the impact of CO 2 and brine leaks on overlying aquifers. The development of these computationally-efficient models and the underlying reactive transport simulations they emulate has been documented elsewhere (Carroll et al., 2014a; Carroll et al., 2014b; Dai et al., 2014 ; Keating et al., 2016). Here in this paper, we seek to demonstrate applicability of ROM-based analysis by considering what types of decisions and aquifermore » types would benefit from the ROM analysis. We present four hypothetical examples where applying ROMs, in ensemble mode, could support decisions during a geologic CO 2 sequestration project. These decisions pertain to site selection, site characterization, monitoring network evaluation, and health impacts. In all cases, we consider potential brine/CO 2 leak rates at the base of the aquifer to be uncertain. We show that derived probabilities provide information relevant to the decision at hand. Although the ROMs were developed using site-specific data from two aquifers (High Plains and Edwards), the models accept aquifer characteristics as variable inputs and so they may have more broad applicability. We conclude that pH and TDS predictions are the most transferable to other aquifers based on the analysis of the nine water quality metrics (pH, TDS, 4 trace metals, 3 organic compounds). Guidelines are presented for determining the aquifer types for which the ROMs should be applicable.« less

Synthesis of a highly dispersed CuO catalyst on CoAl-HT for the epoxidation of styrene.

PubMed

Hu, Rui; Yang, Pengfei; Pan, Yongning; Li, Yunpeng; He, Yufei; Feng, Junting; Li, Dianqing

2017-10-10

A highly dispersed CuO catalyst was prepared by the deposition-precipitation method and evaluated for the catalytic epoxidation of styrene with tert-butyl hydroperoxide (TBHP) as the oxidant under solvent acetonitrile conditions. Compared with MgAl hydrotalcite (MgAl-HT)-, MgO-, TiO 2 -, C-, and MCM-22-supported catalysts, CuO/CoAl-HT exhibited preferable activity and selectivity towards styrene oxide (72% selectivity at 99.5% styrene conversion) due to its high dispersion of CuO and surface area of Cu. The improved dispersion of CuO/CoAl-HT could be ascribed to the nature of HT support, especially the synergistic effect of acidic and basic sites on the surface, which facilitated the formation of highly dispersed CuO species. A structure-performance relationship study indicated that copper(ii) in CuO was the active site for the epoxidation and oxidation of styrene, and that Cu II of rich electronic density favored the improvement of selectivity of styrene oxide. Based on these results, a reaction mechanism was proposed. Moreover, the preferred catalytic performance of CuO/CoAl-HT could be maintained in five reused cycles.

Microbial Communities in Terrestrial CO2 Springs: Insights into the Long-Term Effects of Carbon Sequestration on Subsurface Microorganisms

NASA Astrophysics Data System (ADS)

Santillan, E. F. U.; Major, J. R.; Bennett, P.

2014-12-01

Over long timescales, microbial populations and communities living in environments where CO2 has been sequestered will adapt to this environmental stress. Their presence and activities can have implications for fluid flow, geochemistry, and the fate of the stored CO2. Because of the interplay between microorganisms and environment, many environmental factors beyond CO2 will also contribute to community structure, including groundwater composition and mineralogy. To determine the long-term effect of CO2 on microbial communities, we analyzed terrestrial CO2 springs as analogues to CO2 sequestration in 3 locations in the United States: the Little Grand Wash Fault (LGW), UT; Bravo Dome (BD), NM; and Klickitat Mineral Spring (KMS), WA. These sites differed in multiple aspects such as depth, salinity, Fe content, and mineralogy. LGW and BD were located in the Colorado Plateau in sedimentary locations while KMS was located within the Columbia River Basalt Group. Sites were compared to non-CO2 springs in similar sedimentary formations for comparison. Microbial communities from sedimentary formations were characterized by low diversity and the dominance of the phylotypes Acinetobacter or Burkholderia compared to non-CO2 springs, suggesting community stress and the selection of specific organisms most resilient to CO2. Communities in the basalt formation were more diverse, though diversity is lower than a non-CO2 community sampled from the same formation (Lavalleur and Colwell 2013). Organisms present at the basalt site contained novel lineages, such as the OP candidate phyla. KMS was also the only site containing Archaea, such as Methanoplanus, suggesting CH4 production at depth. Statistical analyses indicate other factors such as depth and nutrient availability may be other factors that can affect diversity in addition to CO2. Growth of a CO2-tolerant organism from LGW also shows organisms in these environments are viable. Results confirm the presence of microbial communities at high PCO2 and suggest that while CO2 is one environmental stress that can lower diversity, many other environmental factors can also influence survival. Lavalleur, H.J., Colwell, F.S., 2013. Microbial characterization of basalt formation waters targeted for geological carbon sequestration. FEMS Microbiology Ecology 85, 62-73.

Complex catalytic behaviors of CuTiO x mixed-oxide during CO oxidation

DOE PAGES

Kim, Hyun You; Liu, Ping

2015-09-21

Mixed metal oxides have attracted considerable attention in heterogeneous catalysis due to the unique stability, reactivity, and selectivity. Here, the activity and stability of the CuTiO x monolayer film supported on Cu(111), CuTiO x/Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiO x is able to stabilize and isolate a single Cu + site on the terrace, which is previously proposed active for CO oxidation. Furthermore, it is not the case, where the reaction via both the Langmuir–Hinshelwood (LH) and the Mars-van Krevelen (M-vK) mechanisms are hindered on such single Cu +more » site. Upon the formation of step-edges, the synergy among Cu δ+ sites, TiO x matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O 2, the surface structure varies, which determines the dominant mechanism. In accordance with our results, the Cu δ+ ion alone does not work well for CO oxidation in the form of single sites, while the synergy among multiple active sites is necessary to facilitate the reaction.« less

Catalysis-dependent selenium incorporation and migration in the nitrogenase active site iron-molybdenum cofactor.

PubMed

Spatzal, Thomas; Perez, Kathryn A; Howard, James B; Rees, Douglas C

2015-12-16

Dinitrogen reduction in the biological nitrogen cycle is catalyzed by nitrogenase, a two-component metalloenzyme. Understanding of the transformation of the inert resting state of the active site FeMo-cofactor into an activated state capable of reducing dinitrogen remains elusive. Here we report the catalysis dependent, site-selective incorporation of selenium into the FeMo-cofactor from selenocyanate as a newly identified substrate and inhibitor. The 1.60 Å resolution structure reveals selenium occupying the S2B site of FeMo-cofactor in the Azotobacter vinelandii MoFe-protein, a position that was recently identified as the CO-binding site. The Se2B-labeled enzyme retains substrate reduction activity and marks the starting point for a crystallographic pulse-chase experiment of the active site during turnover. Through a series of crystal structures obtained at resolutions of 1.32-1.66 Å, including the CO-inhibited form of Av1-Se2B, the exchangeability of all three belt-sulfur sites is demonstrated, providing direct insights into unforeseen rearrangements of the metal center during catalysis.

The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions.

PubMed

Yang, Piaoping; Zhao, Zhi-Jian; Chang, Xiaoxia; Mu, Rentao; Zha, Shenjun; Zhang, Gong; Gong, Jinlong

2018-06-25

Carbon dioxide (CO 2 ) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu 2 O) is a promising catalyst for CO 2 reduction as it can convert CO 2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu 2 O remains under debate because of the complex surface structure of Cu 2 O under reducing conditions, leading to limited guidance in designing improved Cu 2 O catalysts. This paper describes the functionality of surface-bonded hydroxy groups on partially reduced Cu 2 O(111) for the CO 2 reduction reaction (CO 2 RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO 2 RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO 2 RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination-unsaturated Cu (Cu CUS ) sites stabilizes surface-adsorbed COOH*, which is a key intermediate during the CO 2 RR. Moreover, the CO 2 RR was evaluated over Cu 2 O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu 2 O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO 2 RR and suppress the HER. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of 3D quantitative structure-activity relationship methods: Analysis of the in vitro antimalarial activity of 154 artemisinin analogues by hypothetical active-site lattice and comparative molecular field analysis

NASA Astrophysics Data System (ADS)

Woolfrey, John R.; Avery, Mitchell A.; Doweyko, Arthur M.

1998-03-01

Two three-dimensional quantitative structure-activity relationship (3D-QSAR) methods, comparative molecular field analysis (CoMFA) and hypothetical active site lattice (HASL), were compared with respect to the analysis of a training set of 154 artemisinin analogues. Five models were created, including a complete HASL and two trimmed versions, as well as two CoMFA models (leave-one-out standard CoMFA and the guided-region selection protocol). Similar r2 and q2 values were obtained by each method, although some striking differences existed between CoMFA contour maps and the HASL output. Each of the four predictive models exhibited a similar ability to predict the activity of a test set of 23 artemisinin analogues, although some differences were noted as to which compounds were described well by either model.

MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction.

PubMed

Liu, Guoliang; Robertson, Alex W; Li, Molly Meng-Jung; Kuo, Winson C H; Darby, Matthew T; Muhieddine, Mohamad H; Lin, Yung-Chang; Suenaga, Kazu; Stamatakis, Michail; Warner, Jamie H; Tsang, Shik Chi Edman

2017-08-01

The conversion of oxygen-rich biomass into hydrocarbon fuels requires efficient hydrodeoxygenation catalysts during the upgrading process. However, traditionally prepared CoMoS 2 catalysts, although efficient for hydrodesulfurization, are not appropriate due to their poor activity, sulfur loss and rapid deactivation at elevated temperature. Here, we report the synthesis of MoS 2 monolayer sheets decorated with isolated Co atoms that bond covalently to sulfur vacancies on the basal planes that, when compared with conventionally prepared samples, exhibit superior activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene. This higher activity allows the reaction temperature to be reduced from the typically used 300 °C to 180 °C and thus allows the catalysis to proceed without sulfur loss and deactivation. Experimental analysis and density functional theory calculations reveal a large number of sites at the interface between the Co and Mo atoms on the MoS 2 basal surface and we ascribe the higher activity to the presence of sulfur vacancies that are created local to the observed Co-S-Mo interfacial sites.

MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction

NASA Astrophysics Data System (ADS)

Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung; Kuo, Winson C. H.; Darby, Matthew T.; Muhieddine, Mohamad H.; Lin, Yung-Chang; Suenaga, Kazu; Stamatakis, Michail; Warner, Jamie H.; Tsang, Shik Chi Edman

2017-08-01

The conversion of oxygen-rich biomass into hydrocarbon fuels requires efficient hydrodeoxygenation catalysts during the upgrading process. However, traditionally prepared CoMoS2 catalysts, although efficient for hydrodesulfurization, are not appropriate due to their poor activity, sulfur loss and rapid deactivation at elevated temperature. Here, we report the synthesis of MoS2 monolayer sheets decorated with isolated Co atoms that bond covalently to sulfur vacancies on the basal planes that, when compared with conventionally prepared samples, exhibit superior activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene. This higher activity allows the reaction temperature to be reduced from the typically used 300 °C to 180 °C and thus allows the catalysis to proceed without sulfur loss and deactivation. Experimental analysis and density functional theory calculations reveal a large number of sites at the interface between the Co and Mo atoms on the MoS2 basal surface and we ascribe the higher activity to the presence of sulfur vacancies that are created local to the observed Co-S-Mo interfacial sites.

Quantifying CO2 Emissions from Individual Power Plants using OCO-2 Observations

NASA Astrophysics Data System (ADS)

Nassar, R.; Hill, T. G.; McLinden, C. A.; Wunch, D.; Jones, D. B. A.; Crisp, D.

2017-12-01

In order to better manage anthropogenic CO2 emissions, improved methods of quantifying emissions are needed at all spatial scales from the national level down to the facility level. Although the Orbiting Carbon Observatory 2 (OCO-2) satellite was not designed for monitoring power plant emissions, we show that in select cases, CO2 observations from OCO-2 can be used to quantify daily CO2 emissions from individual mid- to large-sized coal power plants by fitting the data to plume model simulations. Emission estimates for US power plants are within 1-13% of reported daily emission values enabling application of the approach to international sites that lack detailed emission information. These results affirm that a constellation of future CO2 imaging satellites, optimized for point sources, could be used for the Monitoring, Reporting and Verification (MRV) of CO2 emissions from individual power plants to support the implementation of climate policies.

Synthesis and CO2/CH4 separation peformance of Bio-MOF-1 membranes

NASA Astrophysics Data System (ADS)

Bohrman, Joseph Allen

The separation of carbon dioxide from natural gas is of great interest from the environmental and energy perspective, respectively. From the environmental point of view, capturing CO2 effectively from power plants can have a positive impact on reducing greenhouse gas emissions. From the energy point of view, CO2 is an undesirable impurity in natural gas wells, with concentrations as high as 70%. Membrane technology can play a major role in making natural gas purification processes economically feasible. A novel membrane composed of Metal-organic-framework material Zn 8(Ad)4(BPDC)6O 2Me2NH2 (Bio-MOF-1) was designed and created to effectively separate CO2/CH4 gas mixtures. The crystalline structure, composition, and textural properties of Bio-MOF-1 membranes were confirmed through x-ray diffractometry, CHN analysis, transmission electron microscopy, adsorption measurements and BET surface area. A secondary seeded growth approach was employed to prepare these membranes on tubular stainless steel porous support. These membranes displayed high CO2 permeances (11.5x10-7 mol / m2 s Pa) and moderate CO2/CH4 separation selectivities (1.2--2.5). The observed selectivities are above the Knudsen selectivity and indicate that the separation is promoted by preferential CO2 adsorption over CH4. This preferential adsorption is attributed to the presence of adeninate amino basic sites present in the Bio-MOF-1 structure. The work demonstrated shows the feasibility of the development of a novel type of membrane that could be promising for diverse molecular gas separations.

Synthesis of π-conjugated polymer consisting of pyrrole and fluorene units by Ru-catalyzed site-selective direct arylation polycondensation.

PubMed

Lu, Wei; Kuwabara, Junpei; Kanbara, Takaki

2013-07-25

Polycondensation of 1-(2-pyrimidinyl)pyrrole with 2,7-dibromo-9,9-dioctylfluorene via Ru-catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2-pyrimidinyl substituent, into the pyrrole monomer induces ortho-metalation and provides the site-selective direct arylation polycondensation at the α-position of pyrrole unit without the protection of β-position. The removal of 2-pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Results from twelve years of continuous monitoring of the soil CO2 flux at the Ketzin CO2 storage pilot site, Germany

NASA Astrophysics Data System (ADS)

Szizybalski, Alexandra; Zimmer, Martin; Pilz, Peter; Liebscher, Axel

2017-04-01

Under the coordination of the GFZ German Research Centre for Geosciences the complete life-cycle of a geological storage site for CO2 has been investigated and studied in detail over the past 12 years at Ketzin near Berlin, Germany. The test site is located at the southern flank of an anticlinal structure. Beginning with an exploration phase in 2004, drilling of the first three wells took place in 2007. From June 2008 to August 2013 about 67 kt of CO2 were injected into Upper Triassic sandstones at a depth of 630 to 650 m overlain by more than 165 m of shaley cap rocks. A comprehensive operational and scientific monitoring program forms the central part of the Ketzin project targeting at the reservoir itself, its overburden or above-zone and the surface. The surface monitoring is done by continuous soil CO2 flux measurements. These already started in 2005, more than three years prior to the injection phase using a survey chamber from LI-COR Inc. Twenty sampling locations were selected in the area of the anticline covering about 3 x 3 km. In order to obtain information on seasonal trends, measurements are performed at least once a month. The data set obtained prior to the injection serves as a basis for comparison with all further measurements during the injection and storage operations [Zimmer et al., 2010]. To refine the monitoring network, eight automatic, permanent soil CO2 flux stations were additionally installed in 2011 in the direct vicinity of the boreholes. Using this system, the CO2 soil flux is measured on an hourly basis. Over the whole monitoring time, soil temperature and moisture are recorded simultaneously and soil samples down to 70 cm depth were studied for their structure, carbon and nitrogen content. ver the whole monitoring time. Both, diurnal and seasonal flux variations can be detected and hence, provide a basis for interpretation of the measured data. Detailed analysis of the long-term monitoring at each station clearly reveals the influence of the soil composition. As most of the sampling positions are located next to agricultural roads and fields, the use of chemicals and harvesting may have an influence on the soil structure and the biology. Soil temperature, rain events and dry periods additionally affect the CO2 flux. Moreover, the microbial controlled increased CO2 production in early fall is also observed to depend on the actual location. Annual mean values of CO2 fluxes range from 10 to 82 t ha-1 a-1. As the CO2 flux measurements significantly reflect the specific site conditions, which can vary locally and over time, long-term trends must be carefully interpreted. Hence, complementary measurements of the soil gas composition were performed at selected locations. Zimmer, M., Pilz, P., Erzinger, J. (2011): Long-term surface carbon dioxide flux monitoring at the Ketzin carbon dioxide storage test site. Environmental Geosciences, 18, 119-130, doi:10.1306/eg.11181010017.

Mathematical programming (MP) model to determine optimal transportation infrastructure for geologic CO2 storage in the Illinois basin

NASA Astrophysics Data System (ADS)

Rehmer, Donald E.

Analysis of results from a mathematical programming model were examined to 1) determine the least cost options for infrastructure development of geologic storage of CO2 in the Illinois Basin, and 2) perform an analysis of a number of CO2 emission tax and oil price scenarios in order to implement development of the least-cost pipeline networks for distribution of CO2. The model, using mixed integer programming, tested the hypothesis of whether viable EOR sequestration sites can serve as nodal points or hubs to expand the CO2 delivery infrastructure to more distal locations from the emissions sources. This is in contrast to previous model results based on a point-to- point model having direct pipeline segments from each CO2 capture site to each storage sink. There is literature on the spoke and hub problem that relates to airline scheduling as well as maritime shipping. A large-scale ship assignment problem that utilized integer linear programming was run on Excel Solver and described by Mourao et al., (2001). Other literature indicates that aircraft assignment in spoke and hub routes can also be achieved using integer linear programming (Daskin and Panayotopoulos, 1989; Hane et al., 1995). The distribution concept is basically the reverse of the "tree and branch" type (Rothfarb et al., 1970) gathering systems for oil and natural gas that industry has been developing for decades. Model results indicate that the inclusion of hubs as variables in the model yields lower transportation costs for geologic carbon dioxide storage over previous models of point-to-point infrastructure geometries. Tabular results and GIS maps of the selected scenarios illustrate that EOR sites can serve as nodal points or hubs for distribution of CO2 to distal oil field locations as well as deeper saline reservoirs. Revenue amounts and capture percentages both show an improvement over solutions when the hubs are not allowed to come into the solution. Other results indicate that geologic storage of CO2 into saline aquifers does not come into solutions selected by the model until the CO 2 emissions tax approaches 50/tonne. CO2 capture and storage begins to occur when the oil price is above 24.42 a barrel based on the constraints of the model. The annual storage capacity of the basin is nearly maximized when the net price of oil is as low as 40 per barrel and the CO2 emission tax is 60/tonne. The results from every subsequent scenario that was examined by this study demonstrate that EOR utilizing anthropogenically captured CO2 will earn net revenue, and thus represents an economically viable option for CO2 storage in the Illinois Basin.

Electrocatalytic Alloys for CO2 Reduction.

PubMed

He, Jingfu; Johnson, Noah J J; Huang, Aoxue; Berlinguette, Curtis P

2018-01-10

Electrochemically reducing CO 2 using renewable energy is a contemporary global challenge that will only be met with electrocatalysts capable of efficiently converting CO 2 into fuels and chemicals with high selectivity. Although many different metals and morphologies have been tested for CO 2 electrocatalysis over the last several decades, relatively limited attention has been committed to the study of alloys for this application. Alloying is a promising method to tailor the geometric and electric environments of active sites. The parameter space for discovering new alloys for CO 2 electrocatalysis is particularly large because of the myriad products that can be formed during CO 2 reduction. In this Minireview, mixed-metal electrocatalyst compositions that have been evaluated for CO 2 reduction are summarized. A distillation of the structure-property relationships gleaned from this survey are intended to help in the construction of guidelines for discovering new classes of alloys for the CO 2 reduction reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Drivers of soil organic matter vulnerability to climate change. Part I: Laboratory incubations of Swiss forest soils and radiocarbon analysis

NASA Astrophysics Data System (ADS)

González Domínguez, Beatriz; Studer, Mirjam S.; Niklaus, Pascal A.; Haghipour, Negar; McIntyre, Cameron; Wacker, Lukas; Zimmermann, Stephan; Walthert, Lorenz; Hagedorn, Frank; Abiven, Samuel

2016-04-01

Given the key role of soil organic carbon (SOC) on climate and greenhouse gas regulation, there is an increasing need to incorporate the carbon (C) feedback between SOC and the atmosphere into earth system models. The evaluation of these models points towards uncertainties on the response of CO2-C fluxes, derived from the decomposition of SOC, to the influence of controls/drivers. SOC vulnerability refers to the likelihood of losing previously stabilized soil organic matter, by the effect of environmental factors. The objective of this study is to produce a SOC vulnerability ranking of soils and to provide new insights into the influence of environmental and soil properties controls. Research on SOC vulnerability tends to focus on climatic controls and neglect the effect of other factors, such as soil geochemistry and mineralogy, on C stabilization/de-stabilization processes. In this work, we hypothesized that climate (mean annual temperature and soil moisture status proxy at the research sites in the period 1981-2010), soil (pH and % clay) and terrain (slope gradient and orientation) characteristics are the main controls of the CO2-C fluxes from SOC. Following a statistics-based approach, we selected 54 forest sites across Switzerland, which cover a broad spectrum of values for the hypothesized controls. Then, we selected the study sites so that the controls are orthogonal to each other; thus, their effect was not confounded. At each site, we collected three non-overlapping topsoil (i.e. 20 cm) composites within 40 x 40 m2 plots. In the laboratory, we sieved fresh soils at 2 mm and run a 2-weeks pre-incubation, before beginning a 6-months aerobic soil incubation under controlled conditions of moisture and temperature. Periodically, we collected NaOH (1M) traps containing the CO2-C derived from microbial heterotrophic respiration. We calculated the cumulative CO2-C respired and the one-pool SOC decomposition rates from the 54 forest sites, and linked these data to the controls. The main result is that soil moisture and pH drive the CO2-C losses, and that temperature, % clay and terrain characteristics do not play a role. We will also present results on the relationship between the bulk soil radiocarbon signature of the 54 forest soils and their CO2-C losses, as a preliminary insight into SOC vulnerability and SOC stabilization processes.

Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

NASA Astrophysics Data System (ADS)

Wang, Y.; Deutscher, N. M.; Palm, M.; Warneke, T.; Notholt, J.; Baker, I.; Berry, J.; Suntharalingam, P.; Jones, N.; Mahieu, E.; Lejeune, B.; Campbell, J. E.; Wolf, A.; Kremser, S.

2015-09-01

Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and inter-annual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential mean to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at three selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The OCS simulations are driven by different land biospheric fluxes to reproduce the seasonality of the measurements. Increasing the plant uptake of Kettle et al. (2002a) by a factor of three resulted in the best comparison with FTIR measurements. However, there are still discrepancies in the latitudinal distribution when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study and compared to measurements. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world.

High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode

DOE PAGES

Song, Yang; Peng, Rui; Hensley, Dale K.; ...

2016-09-28

Carbon dioxide is a pollutant, but also a potential carbon source provided an efficient means to convert it to useful products. Herein we report a nanostructured catalyst for the direct electrochemical reduction of dissolved CO 2 to ethanol with high Faradaic efficiency (63%) and high selectivity (84%). The catalyst is comprised of Cu nanoparticle on a highly textured, N-doped graphene film. Detailed electrochemical analysis and complementary DFT calculations indicate a novel mechanism in which multiple active sites, working sequentially, control the coupling of carbon monoxide radicals and mediate the subsequent electrochemical reduction to alcohol.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, John C.; Mallia, Derek V.; Wu, Dien

Despite the need for researchers to understand terrestrial biospheric carbon fluxes to account for carbon cycle feedbacks and predict future CO 2 concentrations, knowledge of these fluxes at the regional scale remains poor. This is particularly true in mountainous areas, where complex meteorology and lack of observations lead to large uncertainties in carbon fluxes. Yet mountainous regions are often where significant forest cover and biomass are found – i.e., areas that have the potential to serve as carbon sinks. As CO 2 observations are carried out in mountainous areas, it is imperative that they are properly interpreted to yield informationmore » about carbon fluxes. In this paper, we present CO 2 observations at three sites in the mountains of the western US, along with atmospheric simulations that attempt to extract information about biospheric carbon fluxes from the CO 2 observations, with emphasis on the observed and simulated diurnal cycles of CO 2. We show that atmospheric models can systematically simulate the wrong diurnal cycle and significantly misinterpret the CO 2 observations, due to erroneous atmospheric flows as a result of terrain that is misrepresented in the model. This problem depends on the selected vertical level in the model and is exacerbated as the spatial resolution is degraded, and our results indicate that a fine grid spacing of ~4 km or less may be needed to simulate a realistic diurnal cycle of CO 2 for sites on top of the steep mountains examined here in the American Rockies. In conclusion, in the absence of higher resolution models, we recommend coarse-scale models to focus on assimilating afternoon CO 2 observations on mountaintop sites over the continent to avoid misrepresentations of nocturnal transport and influence.« less

Carbon dioxide-selective membranes and their applications in hydrogen processing

NASA Astrophysics Data System (ADS)

Zou, Jian

Fuel cells, which are regarded as a promising energy conversion approach in the 21st century, are now receiving increasing attention worldwide. In most cases, hydrogen is the preferred fuel for fuel cells, especially for proton-exchange membrane fuel cells (PEMFCs). One key issue in the development of PEMFC is how to generate hydrogen from the available hydrocarbon fuels. Most feasible strategies consist of a reforming step followed by the water gas shift (WGS) reaction. The resulting synthesis gas (syngas) still consists of 0.5--1.0% CO, which needs to be reduced to less than 10 ppm to meet the requirement of PEMFCs. Therefore, a further CO clean-up step is usually used to decrease CO concentration. In the present work, new CO2-selective membranes were synthesized and their applications for fuel cell fuel processing and synthesis gas purification were investigated. In order to enhance CO2 transport across membranes, the synthesized membranes contained both mobile and fixed site carriers in crosslinked poly(vinyl alcohol). The effects of crosslinking, membrane composition, feed pressure, water content, and temperature on transport properties were investigated. The membranes have shown a high permeability and a good CO 2/H2 selectivity and maintained their separation performance up to 170°C. One type of these membranes showed a permeability of 8000 Barrers (1 Barrer = 10-10 cm3 (STP).cm/(cm 2.s.cm.Hg)) and a CO2/H2 selectivity of 290 at 110°C. This membrane had a permeability of 1200 Barrers and a CO 2/H2 selectivity of 33 even at 170°C. The applications of the synthesized membranes were demonstrated in a CO2-removal experiment, in which the CO2 concentration in retentate was decreased from 17% to less than 10 ppm. With such membranes, there are several options to reduce the CO concentration of syngas. One option is to develop a WGS membrane reactor, in which both the low temperature WGS reaction and the CO2-removal take place. Another option is to use a proposed process consisting of a CO2-removal membrane module followed by a conventional low-temperature WGS reactor. A third option is to use methanation after the CO2-removal, one of the most widely used processes for the CO clean-up step. Experimental results showed that CO concentration was reduced to below 10 ppm with all three approaches. In the membrane reactor, a CO concentration of less than 10 ppm and a H 2 concentration of greater than 50% (on the dry basis) were achieved at various flow rates of a simulated autothermal reformate. In the proposed CO2-removal/WGS process, with more than 99.5 % CO2 removed from the synthesis gas, the reversible WGS was shifted forward so that the CO concentration was decreased from 1.2% to less than 10 ppm (dry), which is the requirement for PEMFC. The WGS reactor had a gas hourly space velocity of 7650 h-1 at 150°C and the H2 concentration in the outlet was more than 54.7% (dry). The applications of the synthesized CO2-selective membranes for high-pressure synthesis gas purification were also studied. Synthesis gas is the primary source for hydrogen as well as an intermediate for a broad range of chemicals. The separation of CO2 from synthesis gas is a critical step to obtain high purity hydrogen in many industrial plants, especially refinery plants. We studied the synthesized polymeric CO2 -selective membranes for synthesis gas purification at feed pressures higher than 200 psia and temperatures ranging from 100 to 150°C. The effects of feed pressure, microporous support, temperature, and permeate pressure were investigated using a simulated synthesis gas containing 20% carbon dioxide and 80% hydrogen. The membranes synthesized showed best CO2 permeability and CO2/H2 selectivity at 110°C. At a feed pressure of 220 psia, the CO2 permeability and CO2/H2 selectivity reached 756 Barrers and 42, respectively, whereas at a feed pressure of 440 psia, the CO2 permeability was 391 Barrers and the CO 2/H2 selectivity was about 25.

Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH 3 with V 2O 5-WO 3/TiO 2 catalysts

DOE PAGES

He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; ...

2016-04-14

We compared the molecular structures, surface acidity and catalytic activity for NO/NH 3/O 2 SCR of V 2O 5-WO 3/TiO 2 catalysts for two different synthesis methods: co-precipitation of aqueous vanadium and tungsten oxide precursors with TiO(OH) 2 and by incipient wetness impregnation of the aqueous precursors on a reference crystalline TiO 2 support (P25; primarily anatase phase). Bulk analysis by XRD showed that co-precipitation results in small and/or poorly ordered TiO 2(anatase) particles and that VO x and WO x do not form solid solutions with the bulk titania lattice. Surface analysis of the co-precipitated catalyst by High Sensitivity-Lowmore » Energy Ion Scattering (HS-LEIS) confirms that the VO x and WO x are surface segregated for the co-precipitated catalysts. In situ Raman and IR spectroscopy revealed that the vanadium and tungsten oxide components are present as surface mono-oxo O = VO 3 and O = WO 4 sites on the TiO 2 supports. Co-precipitation was shown for the first time to also form new mono-oxo surface VO 4 and WO 4 sites that appear to be anchored at surface defects of the TiO 2 support. IR analysis of chemisorbed ammonia showed the presence of both surface NH 3 * on Lewis acid sites and surface NH 4 +* on Brønsted acid sites. TPSR spectroscopy demonstrated that the specific SCR kinetics was controlled by the redox surface VO 4 species and that the surface kinetics was independent of TiO 2 synthesis method or presence of surface WO 5 sites. SCR reaction studies revealed that the surface WO5 sites possess minimal activity below ~325 °C and their primary function is to increase the adsorption capacity of ammonia. A relationship between the SCR activity and surface acidity was not found. The SCR reaction is controlled by the surface VO 4 sites that initiate the reaction at ~200 °C. The co-precipitated catalysts were always more active than the corresponding impregnated catalysts. Finally, we ascribe the higher activity of the co-precipitated catalysts to the presence of the new surface WO x sites associated surface defects on the TiO 2 support that increase the ammonia adsorption capacity.« less

Improving the Photo-Oxidative Performance of Bi2MoO6 by Harnessing the Synergy between Spatial Charge Separation and Rational Co-Catalyst Deposition.

PubMed

Wu, Xuelian; Hart, Judy N; Wen, Xiaoming; Wang, Liang; Du, Yi; Dou, Shi Xue; Ng, Yun Hau; Amal, Rose; Scott, Jason

2018-03-21

It has been reported that photogenerated electrons and holes can be directed toward specific crystal facets of a semiconductor particle, which is believed to arise from the differences in their surface electronic structures, suggesting that different facets can act as either photoreduction or photo-oxidation sites. This study examines the propensity for this effect to occur in faceted, plate-like bismuth molybdate (Bi 2 MoO 6 ), which is a useful photocatalyst for water oxidation. Photoexcited electrons and holes are shown to be spatially separated toward the {100} and {001}/{010} facets of Bi 2 MoO 6 , respectively, by facet-dependent photodeposition of noble metals (Pt, Au, and Ag) and metal oxides (PbO 2 , MnO x , and CoO x ). Theoretical calculations revealed that differences in energy levels between the conduction bands and valence bands of the {100} and {001}/{010} facets can contribute to electrons and holes being drawn to different surfaces of the plate-like Bi 2 MoO 6 . Utilizing this knowledge, the photo-oxidative capability of Bi 2 MoO 6 was improved by adding an efficient water oxidation co-catalyst, CoO x , to the system, whereby the extent of enhancement was shown to be governed by the co-catalyst location. A greater oxygen evolution occurred when CoO x was selectively deposited on the hole-rich {001}/{010} facets of Bi 2 MoO 6 compared to when CoO x was randomly located across all of the facets. The elevated performance exhibited for the selectively loaded CoO x /Bi 2 MoO 6 was ascribed to the greater opportunity for hole trapping by the co-catalyst being accentuated over other potentially detrimental effects, such as the co-catalyst acting as a recombination medium and/or covering reactive sites. The results indicate that harnessing the synergy between the spatial charge separation and the co-catalyst location on the appropriate facets of plate-like Bi 2 MoO 6 can promote its photocatalytic activity.

Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst.

PubMed

Audemar, Maïté; Ciotonea, Carmen; De Oliveira Vigier, Karine; Royer, Sébastien; Ungureanu, Adrian; Dragoi, Brindusa; Dumitriu, Emil; Jérôme, François

2015-06-08

The hydrogenation of furfural to furfuryl alcohol was performed in the presence of a Co/SBA-15 catalyst. High selectivity (96 %) at a conversion higher than 95 % is reported over this catalytic system. As the conversion of furfural to furfuryl alcohol occurs over metallic Co sites, the effect of reduction temperature, H2 pressure, and reaction temperature were studied. Optimum reaction conditions were: 150 °C, 1.5 h, 2.0 MPa of H2 . The catalyst was recyclable, and furfuryl alcohol was recovered with a purity higher than 90 %. The effect of the solvent concentration was also studied. With a minimum of 50 wt % of solvent, the selectivity to furfuryl alcohol and the conversion of furfural remained high (both over 80 %). Likewise, the activity of the catalyst is maintained even in pure furfural, which confirms the real potential of the proposed catalytic system. This catalyst was also used in the hydrogenation of levulinic acid to produce γ-valerolactone selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational evaluation of sub-nanometer cluster activity of singly exposed copper atom with various coordinative environment in catalytic CO2 transformation

NASA Astrophysics Data System (ADS)

Shanmugam, Ramasamy; Thamaraichelvan, Arunachalam; Ganesan, Tharumeya Kuppusamy; Viswanathan, Balasubramanian

2017-02-01

Metal cluster, at sub-nanometer level has a unique property in the activation of small molecules, in contrast to that of bulk surface. In the present work, singly exposed active site of copper metal cluster at sub-nanometer level was designed to arrive at the energy minimised configurations, binding energy, electrostatic potential map, frontier molecular orbitals and partial density of states. The ab initio molecular dynamics was carried out to probe the catalytic nature of the cluster. Further, the stability of the metal cluster and its catalytic activity in the electrochemical reduction of CO2 to CO were evaluated by means of computational hydrogen electrode via calculation of the free energy profile using DFT/B3LYP level of theory in vacuum. The activity of the cluster is ascertained from the fact that the copper atom, present in a two coordinative environment, performs a more selective conversion of CO2 to CO at an applied potential of -0.35 V which is comparatively lower than that of higher coordinative sites. The present study helps to design any sub-nano level metal catalyst for electrochemical reduction of CO2 to various value added chemicals.

Carbon dioxide and methane measurements from the Los Angeles Megacity Carbon Project - Part 1: calibration, urban enhancements, and uncertainty estimates

NASA Astrophysics Data System (ADS)

Verhulst, Kristal R.; Karion, Anna; Kim, Jooil; Salameh, Peter K.; Keeling, Ralph F.; Newman, Sally; Miller, John; Sloop, Christopher; Pongetti, Thomas; Rao, Preeti; Wong, Clare; Hopkins, Francesca M.; Yadav, Vineet; Weiss, Ray F.; Duren, Riley M.; Miller, Charles E.

2017-07-01

We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban-scale CO2 and CH4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four extra-urban sites including two marine sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one continental site located in Victorville (VIC), in the high desert northeast of LA, and one continental/mid-troposphere site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within ˜ 1 ppm CO2 and ˜ 10 ppb CH4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. Urban and suburban sites show moderate to large CO2 and CH4 enhancements relative to a marine background estimate. The USC (University of Southern California) site near downtown LA exhibits median hourly enhancements of ˜ 20 ppm CO2 and ˜ 150 ppb CH4 during 2015 as well as ˜ 15 ppm CO2 and ˜ 80 ppb CH4 during mid-afternoon hours (12:00-16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO2 and 1 ppb CH4 based on the repeated standard gas measurements from the LA sites during the last 2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the single-point calibration method; however, the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The background uncertainty for the marine background estimate is ˜ 10 and ˜ 15 % of the median mid-afternoon enhancement near downtown LA for CO2 and CH4, respectively. Overall, analytical and background uncertainties are small relative to the local CO2 and CH4 enhancements; however, our results suggest that reducing the uncertainty to less than 5 % of the median mid-afternoon enhancement will require detailed assessment of the impact of meteorology on background conditions.

In situ DRIFTS study of O3 adsorption on CaO, γ-Al2O3, CuO, α-Fe2O3 and ZnO at room temperature for the catalytic ozonation of cinnamaldehyde

NASA Astrophysics Data System (ADS)

Wu, Jianfeng; Su, Tongming; Jiang, Yuexiu; Xie, Xinling; Qin, Zuzeng; Ji, Hongbing

2017-08-01

In situ DRIFTS were conducted to identify adsorbed ozone and/or adsorbed oxygen species on CaO, ZnO, γ-Al2O3, CuO and α-Fe2O3 surfaces at room temperature. Samples were characterized by means of TG, XRD, N2 adsorption-desorption, pyridine-IR, nitrobenzene-IR, chloroform-IR, and CO2-TPD. Pyridine-DRIFTS measurements evidence two kinds of acid sites in all the samples. Nitrobenzene, chloroform-DRIFTS, and CO2-TPD reveal that there are large amounts of medium-strength base sites on all the metal oxides, and only CaO, ZnO, and γ-Al2O3 have strong base sites. And the benzaldehyde selectivity was increased in the same order of the alkalinity of the metal oxides. With weaker sites, ozone molecules form coordinative complexes bound via the terminal oxygen atom, observed by vibrational frequencies at 2095-2122 and 1026-1054 cm-1. The formation of ozonide O3- at 790 cm-1, atomic oxygen at 1317 cm-1, and superoxide O2- at 1124 cm-1 was detected; these species are believed to be intermediates of O3 decomposition on strong acid/base sites. The adsorption of ozone on metal oxides is a weak adsorption, and other gases, such as CO2, will compete with O3 adsorption. The mechanism of cinnamaldehyde ozonation at room temperature over CaO shows that cinnamaldehyde can not only be oxidized into cinnamic acid, but also be further oxidized into benzaldehyde, benzoic acid, maleic anhydride, and ultimately mineralized to CO2 in the presence of O3.

Selective photocatalytic reduction of CO2 to methanol in CuO-loaded NaTaO3 nanocubes in isopropanol

PubMed Central

Xiang, Tianyu; Chen, Jingshuai; Wang, Yuwen; Yin, Xiaohong; Shao, Xiao

2016-01-01

Summary A series of NaTaO3 photocatalysts were prepared with Ta2O5 and NaOH via a hydrothermal method. CuO was loaded onto the surface of NaTaO3 as a cocatalyst by successive impregnation and calcination. The obtained photocatalysts were characterized by XRD, SEM, UV–vis, EDS and XPS and used to photocatalytically reduce CO2 in isopropanol. This worked to both absorb CO2 and as a sacrificial reagent to harvest CO2 and donate electrons. Methanol and acetone were generated as the reduction product of CO2 and the oxidation product of isopropanol, respectively. NaTaO3 nanocubes loaded with 2 wt % CuO and synthesized in 2 mol/L NaOH solution showed the best activity. The methanol and acetone yields were 137.48 μmol/(g·h) and 335.93 μmol/(g·h), respectively, after 6 h of irradiation. Such high activity could be attributed to the good crystallinity, morphology and proper amount of CuO loading, which functioned as reductive sites for selective formation of methanol. The reaction mechanism was also proposed and explained by band theory. PMID:27335766

A 5 Year Study of Carbon Fluxes from a Restored English Blanket Bog

NASA Astrophysics Data System (ADS)

Worrall, F.; Dixon, S.; Evans, M.

2014-12-01

This study aimed to measure the effects of ecological restoration on blanket peat water table depths, DOC concentrations and CO2 fluxes. In April 2003 the Bleaklow Plateau, an extensive area of deep blanket peat in the Peak District National Park, northern England, was devegetated by a wildfire. As a result the area was selected for large scale restoration. In this study we considered a 5-year study of four restored sites in comparison to both an unrestored, bare peat control and to vegetated control that did not require restoration. Results suggested that sites with revegetation alongside slope stabilisation had the highest rates of photosynthesis and were the largest net (daylight hours) sinks of CO2. Bare sites were the largest net sources of CO2 and had the deepest water table depths. Sites with gully wall stabilisation were between 5-8 times more likely to be net CO2 sinks than the bare sites. Revegetation without gully flow blocking using plastic dams did not have a large effect on water table depths in and around the gullies investigated whereas a blocked gully had water table depths comparable to a naturally revegetating gully. A ten centimetre lowering in water table depth decreased the probability of observing a net CO2 sink, on a given site, by up to 30%. With respect to DOC the study showed that the average soil porewater DOC concentration on the restored sites rose significantly over the 5 year study representing a 34% increase relative to the vegetated control and an 11% increase relative to the unrestored, bare control. Soil pore water concentrations were not significantly different from surface runoff DOC concentrations and therefore restoration as conducted by this study would have contributed to water quality deterioration in the catchment. The most important conclusion of this research was that restoration interventions were apparently effective at increasing the likelihood of net CO2 sink behaviour and raising water tables on degraded, climatically marginal blanket bog. However, had water table restoration been conducted alongside revegetation then a significant decline in DOC concentrations could have also been realised.

Amino-functionalized surface modification of polyacrylonitrile hollow fiber-supported polydimethylsiloxane membranes

NASA Astrophysics Data System (ADS)

Hu, Leiqing; Cheng, Jun; Li, Yannan; Liu, Jianzhong; Zhou, Junhu; Cen, Kefa

2017-08-01

This study aimed to improve surface polarity of polydimethylsiloxane (PDMS) membranes and provide surface active sites which were easy to react with other chemicals. 3-Aminopropyltriethoxysilane (APTES) containing an amino group was introduced into a PDMS membrane by crosslinking to prepare polyacrylonitrile hollow fiber-supported PDMS membranes with an amino-functionalized surface. Fourier transform infrared and X-ray photoelectron spectroscopic analyses proved the existence of APTES and its amino group in the PDMS membrane. The concentration of N atoms on the PDMS membrane surface reached ∼6% when the mass ratio of APTES/PDMS oligomer in the PDMS coating solution was increased to 4/3. The water contact angle decreased from ∼114° to ∼87.5°, indicating the improved surface polarization of the PDMS membrane. The density and swelling degree of the PDMS membrane decreased and increased, respectively, with increasing APTES content in PDMS. This phenomenon increased CO2 permeability and decreased CO2/H2 selectivity, CO2/CH4 selectivity, and CO2/N2 selectivity. When the mass ratio of APTES/PDMS oligomer was increased from 0 to 4/3, the CO2 permeation rate of the hollow fiber-supported PDMS membranes initially decreased from ∼2370 GPU to ∼860 GPU and then increased to ∼2000 GPU due to the change in coating solution viscosity.

One-Pot Synthesis of Mesoporous Ni-Ti-Al Ternary Oxides: Highly Active and Selective Catalysts for Steam Reforming of Ethanol.

PubMed

Gonçalves, Alexandre A S; Faustino, Patrícia B; Assaf, José M; Jaroniec, Mietek

2017-02-22

One-pot synthesis of nanostructured ternary oxides of Ni, Al, and Ti was designed and performed via evaporation induced self-assembly (EISA). For the purpose of comparison, analogous oxides were also prepared by the impregnation method. The resulting materials were applied in two catalytic reactions: steam reforming of ethanol (SRE) for H 2 production (subjected to prior activation with H 2 ) and ethanol dehydration (ED; used without prior activation), to in situ analyze carbon accumulation by ethylene depletion when ethanol interacts with acidic sites present on the support. Modification of Ni-Al mixed oxides with titania was shown to have several benefits. CO 2 , NH 3 , and propylamine sorption data indicate a decrease in the strength of acidic and basic sites after addition of titania, which in turn slowed down the carbon accumulation during the ED reaction. These changes in interactions between ethanol and byproducts with the support led to different reaction pathways in SRE, indicating that the catalysts obtained by EISA with titania addition showed higher ethylene selectivity and CO 2 /CO ratios. The opposite was observed for the impregnated catalysts, which were less coke-stable during ED reactions and showed no ethylene selectivity in SRE. Carbon formed during ED reactions was shown to be thermodynamically less favorable and easier to decompose in the presence of titania. All catalysts studied displayed similar and high selectivities (∼80%) and yields (∼5.3 mol H2 /mol ethanol ) toward H 2 , which place them among the most active and selective catalysts for SRE. These results indicate the importance of tailoring the support surface acidity to achieve high reforming performance and higher selectivity toward SRE, one of the key processes to produce cleaner and efficient fuels. For an efficient reforming process, the yield of byproducts is low but still they affect the catalyst stability in the long-run, thus this work may impact future studies toward development of near-zero coke catalysts.

CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

PubMed

Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

2018-06-01

CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

A spin transition mechanism for cooperative adsorption in metal-organic frameworks

NASA Astrophysics Data System (ADS)

Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

2017-10-01

Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

Applicability of aquifer impact models to support decisions at CO2 sequestration sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keating, Elizabeth; Bacon, Diana; Carroll, Susan

2016-09-01

The National Risk Assessment Partnership has developed a suite of tools to assess and manage risk at CO2 sequestration sites (www.netldoe.gov/nrap). This capability includes polynomial or look-up table based reduced-order models (ROMs) that predict the impact of CO2 and brine leaks on overlying aquifers. The development of these computationally-efficient models and the underlying reactive transport simulations they emulate has been documented elsewhere (Carroll et al., 2014, Dai et al., 2014, Keating et al., 2015). The ROMs reproduce the ensemble behavior of large numbers of simulations and are well-suited to applications that consider a large number of scenarios to understand parametermore » sensitivity and uncertainty on the risk of CO2 leakage to groundwater quality. In this paper, we seek to demonstrate applicability of ROM-based ensemble analysis by considering what types of decisions and aquifer types would benefit from the ROM analysis. We present four hypothetical four examples where applying ROMs, in ensemble mode, could support decisions in the early stages in a geologic CO2 sequestration project. These decisions pertain to site selection, site characterization, monitoring network evaluation, and health impacts. In all cases, we consider potential brine/CO2 leak rates at the base of the aquifer to be uncertain. We show that derived probabilities provide information relevant to the decision at hand. Although the ROMs were developed using site-specific data from two aquifers (High Plains and Edwards), the models accept aquifer characteristics as variable inputs and so they may have more broad applicability. We conclude that pH and TDS predictions are the most transferable to other aquifers based on the analysis of the nine water quality metrics (pH, TDS, 4 trace metals, 3 organic compounds). Guidelines are presented for determining the aquifer types for which the ROMs should be applicable.« less

Role of ZrO 2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Gregory R.; Bell, Alexis T.

2015-11-17

The effects of Zr promotion on the structure and performance of Co-based Fischer-Tropsch synthesis (FTS) catalysts were investigated. Inclusion of Zr in the catalysts was found to increase the FTS turnover frequency and the selectivity to C 5+ hydrocarbons and to decrease the selectivity to methane under most operating conditions. These improvements to the catalytic performance are a function of Zr loading up to an atomic ratio of Zr/Co = 1.0, above which the product selectivity is insensitive to higher concentrations of the promoter. Characterization of the Co nanoparticles by different methods demonstrated that the optimal Zr loading corresponds tomore » half monolayer coverage of the Co surface by the promoter. Measurements of the rate of FTS at different pressures and temperatures established that the kinetics data for both the Zr-promoted and unpromoted catalysts are described by a two-parameter Langmuir-Hinshelwood expression. The parameters used to fit this rate law to the experimental data indicate that the apparent rate coefficient and the CO adsorption constant for the Zr-promoted catalysts are higher than those for the unpromoted catalyst. Elemental mapping by means of STEM-EDS provided evidence that Zr is highly dispersed over the catalyst surface and has limited preference for association with the Co nanoparticles. In situ X-ray absorption spectroscopy confirmed the absence of mixing between the Zr and Co in the nanoparticles. Here, these results suggest that Zr exists as a partial layer of ZrO 2 on the surface of the Co metal nanoparticles. Accordingly, it is proposed that Zr promotion effects originate from sites of enhanced activity at the interface between Co and ZrO 2. The possibility that ZrO 2 acts as a Lewis acid to assist in CO dissociation as well as to increase the ratio of CO to H adsorbed on the catalyst surface is discussed.« less

Making synthetic mudstone: Parametric resedimentation studies at high effective stress to determine controls on breakthrough pressure and permeability

NASA Astrophysics Data System (ADS)

Guiltinan, E. J.; Cardenas, M. B.; Cockrell, L.; Espinoza, N.

2017-12-01

The geologic sequestration of CO2 is widely considered a potential solution for decreasing anthropogenic atmospheric CO2 emissions. As CO2 rises buoyantly within a reservoir it pools beneath a caprock and a pressure is exerted upon the pores of the caprock proportionally to the height of the pool. The breakthrough pressure is the point at which CO2 begins to flow freely across the caprock. Understanding the mineralogical and grain size controls on breakthrough pressure is important for screening the security of CO2 sequestration sites. However, breakthrough pressure and permeability measurements on caprocks are difficult to conduct in a systematic manner given the variability in and heterogeneity of naturally occurring mudstones and shales causing significant noise and scatter in the literature. Recent work has even revealed the ability for CO2 to pass through thin shale beds at relatively low pressures. To broaden the understanding of shale breakthrough and permeability, we developed an approach that allows for the creation of resedimented mudstones at high effective stresses. Resedimented samples also include calcium carbonate cement. Using this technique, we explore the controls on entry pressure, breakthrough pressure, and permeability of synthetic mudstones. Understanding the effect of mineralogy and grain size on the permeability and breakthrough pressure of mudstones at reservoir stresses will help in the selection and uncertainty quantification of secure CO2 storage sites.

Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach.

PubMed

Yazaydin, A Ozgür; Snurr, Randall Q; Park, Tae-Hong; Koh, Kyoungmoo; Liu, Jian; Levan, M Douglas; Benin, Annabelle I; Jakubczak, Paulina; Lanuza, Mary; Galloway, Douglas B; Low, John J; Willis, Richard R

2009-12-30

A diverse collection of 14 metal-organic frameworks (MOFs) was screened for CO(2) capture from flue gas using a combined experimental and modeling approach. Adsorption measurements are reported for the screened MOFs at room temperature up to 1 bar. These data are used to validate a generalized strategy for molecular modeling of CO(2) and other small molecules in MOFs. MOFs possessing a high density of open metal sites are found to adsorb significant amounts of CO(2) even at low pressure. An excellent correlation is found between the heat of adsorption and the amount of CO(2) adsorbed below 1 bar. Molecular modeling can aid in selection of adsorbents for CO(2) capture from flue gas by screening a large number of MOFs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Hyun You; Liu, Ping

Mixed metal oxides have attracted considerable attention in heterogeneous catalysis due to the unique stability, reactivity, and selectivity. Here, the activity and stability of the CuTiO x monolayer film supported on Cu(111), CuTiO x/Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiO x is able to stabilize and isolate a single Cu + site on the terrace, which is previously proposed active for CO oxidation. Furthermore, it is not the case, where the reaction via both the Langmuir–Hinshelwood (LH) and the Mars-van Krevelen (M-vK) mechanisms are hindered on such single Cu +more » site. Upon the formation of step-edges, the synergy among Cu δ+ sites, TiO x matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O 2, the surface structure varies, which determines the dominant mechanism. In accordance with our results, the Cu δ+ ion alone does not work well for CO oxidation in the form of single sites, while the synergy among multiple active sites is necessary to facilitate the reaction.« less

Characterization of Co(III) EDTA-Reducing Bacteria in Metal- and Radionuclide-Contaminated Groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Weimin; Gentry, Terry J; Mehlhorn, Tonia L

The Waste Area Grouping 5 (WAG5) site at Oak Ridge National Laboratory has a potential to be a field site for evaluating the effectiveness of various bioremediation approaches and strategies. The site has been well studied in terms of its geological and geochemical properties over the past decade. However, despite the importance of microorganisms in bioremediation processes, the microbiological populations at the WAG5 site and their potential in bioremediation have not been similarly evaluated. In this study, we initiated research to characterize the microbial populations in WAG5 groundwater. Approximately 100 isolates from WAG5 groundwater were isolated and selected based onmore » colony morphology. Fifty-five unique isolates were identified by BOX-PCR and subjected to further characterization. 16S rRNA sequences indicated that these isolates belong to seventeen bacterial genera including Alcaligenes (1 isolate), Aquamonas (1), Aquaspirillum (1), Bacillus (10), Brevundimonas (5), Caulobacter (7), Dechloromonas (2), Janibacter (1), Janthinobacterium (2), Lactobacillus (1), Paenibacillus (4), Pseudomonas (9), Rhodoferax (1), Sphingomonas (1), Stenotrophomonas (6), Variovorax (2), and Zoogloea (1). Metal respiration assays identified several isolates, which phylogenically belong or are close to Caulobacter, Stenotrophomonas, Bacillus, Paenibacillus and Pseudomonas, capable of reducing Co(III)EDTA- to Co(II)EDTA{sup 2-} using the defined M1 medium under anaerobic conditions. In addition, using WAG5 groundwater directly as the inoculants, we found that organisms associated with WAG5 groundwater can reduce both Fe(III) and Co(III) under anaerobic conditions. Further assays were then performed to determine the optimal conditions for Co(III) reduction. These assays indicated that addition of various electron donors including ethanol, lactate, methanol, pyruvate, and acetate resulted in metal reduction. These experiments will provide useful background information for future bioremediation field experiments at the WAG5 site.« less

Exploring the structure and function of Thermotoga maritima CorA reveals the mechanism of gating and ion selectivity in Co2+/Mg2+ transport

PubMed Central

Nordin, Nurhuda; Guskov, Albert; Phua, Terri; Sahaf, Newsha; Xia, Yu; Lu, Siyan; Eshaghi, Hojjat; Eshaghi, Said

2013-01-01

The CorA family of divalent cation transporters utilizes Mg2+ and Co2+ as primary substrates. The molecular mechanism of its function, including ion selectivity and gating, has not been fully characterized. Recently we reported a new structure of a CorA homologue from Methanocaldococcus jannaschii, which provided novel structural details that offered the conception of a unique gating mechanism involving conversion of an open hydrophilic gate into a closed hydrophobic one. In the present study we report functional evidence for this novel gating mechanism in the Thermotoga maritima CorA together with an improved crystal structure of this CorA to 2.7 Å (1 Å=0.1 nm) resolution. The latter reveals the organization of the selectivity filter to be similar to that of M. jannaschii CorA and also the previously unknown organization of the second signature motif of the CorA family. The proposed gating is achieved by a helical rotation upon the binding of a metal ion substrate to the regulatory binding sites. Additionally, our data suggest that the preference of this CorA for Co2+ over Mg2+ is controlled by the presence of threonine side chains in the channel. Finally, the roles of the intracellular metal-binding sites have been assigned to increased thermostability and regulation of the gating. These mechanisms most likely apply to the entire CorA family as they are regulated by the highly conserved amino acids. PMID:23425532

Transcription Factor Binding Site Enrichment Analysis in Co-Expression Modules in Celiac Disease

PubMed Central

Romero-Garmendia, Irati; Jauregi-Miguel, Amaia; Plaza-Izurieta, Leticia; Cros, Marie-Pierre; Legarda, Maria; Irastorza, Iñaki; Herceg, Zdenko; Fernandez-Jimenez, Nora

2018-01-01

The aim of this study was to construct celiac co-expression patterns at a whole genome level and to identify transcription factors (TFs) that could drive the gliadin-related changes in coordination of gene expression observed in celiac disease (CD). Differential co-expression modules were identified in the acute and chronic responses to gliadin using expression data from a previous microarray study in duodenal biopsies. Transcription factor binding site (TFBS) and Gene Ontology (GO) annotation enrichment analyses were performed in differentially co-expressed genes (DCGs) and selection of candidate regulators was performed. Expression of candidates was measured in clinical samples and the activation of the TFs was further characterized in C2BBe1 cells upon gliadin challenge. Enrichment analyses of the DCGs identified 10 TFs and five were selected for further investigation. Expression changes related to active CD were detected in four TFs, as well as in several of their in silico predicted targets. The activation of TFs was further characterized in C2BBe1 cells upon gliadin challenge, and an increase in nuclear translocation of CAMP Responsive Element Binding Protein 1 (CREB1) and IFN regulatory factor-1 (IRF1) in response to gliadin was observed. Using transcriptome-wide co-expression analyses we are able to propose novel genes involved in CD pathogenesis that respond upon gliadin stimulation, also in non-celiac models. PMID:29748492

Transcription Factor Binding Site Enrichment Analysis in Co-Expression Modules in Celiac Disease.

PubMed

Romero-Garmendia, Irati; Garcia-Etxebarria, Koldo; Hernandez-Vargas, Hector; Santin, Izortze; Jauregi-Miguel, Amaia; Plaza-Izurieta, Leticia; Cros, Marie-Pierre; Legarda, Maria; Irastorza, Iñaki; Herceg, Zdenko; Fernandez-Jimenez, Nora; Bilbao, Jose Ramon

2018-05-10

The aim of this study was to construct celiac co-expression patterns at a whole genome level and to identify transcription factors (TFs) that could drive the gliadin-related changes in coordination of gene expression observed in celiac disease (CD). Differential co-expression modules were identified in the acute and chronic responses to gliadin using expression data from a previous microarray study in duodenal biopsies. Transcription factor binding site (TFBS) and Gene Ontology (GO) annotation enrichment analyses were performed in differentially co-expressed genes (DCGs) and selection of candidate regulators was performed. Expression of candidates was measured in clinical samples and the activation of the TFs was further characterized in C2BBe1 cells upon gliadin challenge. Enrichment analyses of the DCGs identified 10 TFs and five were selected for further investigation. Expression changes related to active CD were detected in four TFs, as well as in several of their in silico predicted targets. The activation of TFs was further characterized in C2BBe1 cells upon gliadin challenge, and an increase in nuclear translocation of CAMP Responsive Element Binding Protein 1 (CREB1) and IFN regulatory factor-1 (IRF1) in response to gliadin was observed. Using transcriptome-wide co-expression analyses we are able to propose novel genes involved in CD pathogenesis that respond upon gliadin stimulation, also in non-celiac models.

Selective Transformation of CO2 to CO at a Single Nickel Center.

PubMed

Yoo, Changho; Kim, Yeong-Eun; Lee, Yunho

2018-05-15

Carbon dioxide conversion mediated by transition metal complexes continues to attract much attention because of its future potential utilization as a nontoxic and inexpensive C1 source for the chemical industry. Given the presence of nickel in natural systems that allow for extremely efficient catalysis, albeit in an Fe cluster arrangement, studies that focus on selective CO 2 conversion with synthetic nickel species are currently of considerable interest in our group. In this Account, the selective conversion of CO 2 to carbon monoxide occurring at a single nickel center is discussed. The chemistry is based on a series of related nickel pincer complexes with attention to the uniqueness of the coordination geometry, which is crucial in allowing for particular reactivity toward CO 2 . Our research is inspired by the efficient enzymatic CO 2 catalysis occurring at the active site of carbon monoxide dehydrogenase. Since the binding and reactivity toward CO 2 are controlled in part by the geometry of a L 3 Ni scaffold, we have explored the chemistry of low-valent nickel supported by PP Me P and PNP ligands, in which a pseudotetrahedral or square-planar geometry is accommodated. Two isolated nickel-CO 2 adducts, (PP Me P)Ni(η 2 -CO 2 -κ C) (2) and {Na(12-C-4) 2 }{(PNP)Ni(η 1 -CO 2 -κ C)} (7), clearly demonstrate that the geometry of the nickel ion is crucial in the binding of CO 2 and its level of activation. In the case of a square-planar nickel center supported by a PNP ligand, a series of bimetallic metallacarboxylate Ni-μ-CO 2 -κ C, O-M species (M = H, Na, Ni, Fe) were synthesized, and their structural features and reactivity were studied. Protonation cleaves the C-O bond, resulting in the formation of a nickel(II) monocarbonyl complex. By sequential reduction, the corresponding mono- and zero-valent Ni-CO species were produced. The reactivities of three nickel carbonyl species toward various iodoalkanes and CO 2 were explored to address whether their corresponding reactivities could be controlled by the number of valence d electrons. In particular, a (PNP)Ni(0)-CO species (13) shows immediate reactivity toward CO 2 but displays multiple product formation. By incorporation of a -CMe 2 - bridging unit, a structurally rigidified acri PNP ligand was newly designed and produced. This ligand modification was successful in preparing the T-shaped nickel(I) metalloradical species 9 exhibiting open-shell reactivity due to the sterically exposed nickel center possessing a half-filled d x 2 - y 2 orbital. More importantly, the selective addition of CO 2 to a nickel(0)-CO species was enabled to afford a nickel(II)-carboxylate species (22) with the expulsion of CO(g). Finally, the ( acri PNP)Ni system provides a synthetic cycle in the study of the selective conversion of CO 2 to CO that involves two-electron reduction of Ni-CO followed by the direct addition of CO 2 to release the coordinated CO ligand.

New Insights into Reaction Mechanisms of Ethanol Steam Reforming on Co-ZrO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Junming; Karim, Ayman M.; Mei, Donghai

2015-01-01

The reaction pathway of ethanol steam reforming on Co-ZrO2 has been identified and the active sites associated with each step are proposed. Ethanol is converted to acetaldehyde and then to acetone, followed by acetone steam reforming. More than 90% carbon was found to follow this reaction pathway. N2-Sorption, X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR), in situ X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy, as well as theoretical Density Functional Theory (DFT) calculations have been employed to identify the structure and functionality of the catalysts, which was further used to correlate their performance in ESR. It was found that metallicmore » cobalt is mainly responsible for the acetone steam reforming reactions; while, CoO and basic sites on the support play a key role in converting ethanol to acetone via dehydrogenation and condensation/ketonization reaction pathways. The current work provides fundamental understanding of the ethanol steam reforming reaction mechanisms on Co-ZrO2 catalysts and sheds light on the rational design of selective and durable ethanol steam reforming catalysts.« less

Habitat selection in a rocky landscape: experimentally decoupling the influence of retreat site attributes from that of landscape features.

PubMed

Croak, Benjamin M; Pike, David A; Webb, Jonathan K; Shine, Richard

2012-01-01

Organisms selecting retreat sites may evaluate not only the quality of the specific shelter, but also the proximity of that site to resources in the surrounding area. Distinguishing between habitat selection at these two spatial scales is complicated by co-variation among microhabitat factors (i.e., the attributes of individual retreat sites often correlate with their proximity to landscape features). Disentangling this co-variation may facilitate the restoration or conservation of threatened systems. To experimentally examine the role of landscape attributes in determining retreat-site quality for saxicolous ectotherms, we deployed 198 identical artificial rocks in open (sun-exposed) sites on sandstone outcrops in southeastern Australia, and recorded faunal usage of those retreat sites over the next 29 months. Several landscape-scale attributes were associated with occupancy of experimental rocks, but different features were important for different species. For example, endangered broad-headed snakes (Hoplocephalus bungaroides) preferred retreat sites close to cliff edges, flat rock spiders (Hemicloea major) preferred small outcrops, and velvet geckos (Oedura lesueurii) preferred rocks close to the cliff edge with higher-than-average sun exposure. Standardized retreat sites can provide robust experimental data on the effects of landscape-scale attributes on retreat site selection, revealing interspecific divergences among sympatric taxa that use similar habitats.

Multiphase modeling of geologic carbon sequestration in saline aquifers.

PubMed

Bandilla, Karl W; Celia, Michael A; Birkholzer, Jens T; Cihan, Abdullah; Leister, Evan C

2015-01-01

Geologic carbon sequestration (GCS) is being considered as a climate change mitigation option in many future energy scenarios. Mathematical modeling is routinely used to predict subsurface CO2 and resident brine migration for the design of injection operations, to demonstrate the permanence of CO2 storage, and to show that other subsurface resources will not be degraded. Many processes impact the migration of CO2 and brine, including multiphase flow dynamics, geochemistry, and geomechanics, along with the spatial distribution of parameters such as porosity and permeability. In this article, we review a set of multiphase modeling approaches with different levels of conceptual complexity that have been used to model GCS. Model complexity ranges from coupled multiprocess models to simplified vertical equilibrium (VE) models and macroscopic invasion percolation models. The goal of this article is to give a framework of conceptual model complexity, and to show the types of modeling approaches that have been used to address specific GCS questions. Application of the modeling approaches is shown using five ongoing or proposed CO2 injection sites. For the selected sites, the majority of GCS models follow a simplified multiphase approach, especially for questions related to injection and local-scale heterogeneity. Coupled multiprocess models are only applied in one case where geomechanics have a strong impact on the flow. Owing to their computational efficiency, VE models tend to be applied at large scales. A macroscopic invasion percolation approach was used to predict the CO2 migration at one site to examine details of CO2 migration under the caprock. © 2015, National Ground Water Association.

Satellite assisted aerosol correlation in a sequestered CO2 leakage controlled site

NASA Astrophysics Data System (ADS)

Landulfo, Eduardo; da Silva Lopes, Fábio J.; Nakaema, Walter M.; de Medeiros, José A. G.; Moreira, Andrea

2014-10-01

Currently one of the main challenges in CO2 storage research is to grant the development, testing and validation of accurate and efficient Measuring, Monitoring and Verification (MMV) techniques to be deployed at the final storage site, targeting maximum storage efficiency at the minimal leakage risk levels. For such task a mimetic sequestration site has been deployed in Florianopolis, Brazil, in order to verify the performance of monitoring plataforms to detect and quantify leakages of ground injected CO2, namely a Cavity Ring Down System (CRDS) - Los Gatos Research - an Eddy Covariance System (Campbell Scientific and Irgason) and meteorological tower for wind, humidity, precipitation and temperature monitoring onsite. The measurement strategy for detecting CO2 leakages can be very challenging since environmental and phytogenic influence can be very severe and play a role on determining if the values measured are unambiguous or not. One external factor to be considered is the amount of incoming solar radiation which will be the driving force for the whole experimental setup and following this reasoning the amount of aerosols in the atmospheric column can be a determinant factor influencing the experimental results. Thus the investigation of measured fluxes CO2 and its concentration with the aforementioned experimental instruments and their correlation with the aerosol data should be taken into account by means of satellite borne systems dedicated to measure aerosol vertical distribution and its optical properties, in this study we have selected CALIPSO and MODIS instrumentation to help on deriving the aerosol properties and CO2 measurements.

Imidazolium- and Triazine-Based Porous Organic Polymers for Heterogeneous Catalytic Conversion of CO2 into Cyclic Carbonates.

PubMed

Zhong, Hong; Su, Yanqing; Chen, Xingwei; Li, Xiaoju; Wang, Ruihu

2017-12-22

CO 2 adsorption and concomitant catalytic conversion into useful chemicals are promising approaches to alleviate the energy crisis and effects of global warming. This is highly desirable for developing new types of heterogeneous catalytic materials containing CO 2 -philic groups and catalytic active sites for CO 2 chemical transformation. Here, we present an imidazolium- and triazine-based porous organic polymer with counter chloride anion (IT-POP-1). The porosity and CO 2 affinity of IT-POP-1 may be modulated at the molecular level through a facile anion-exchange strategy. Compared with the post-modified polymers with iodide and hexafluorophosphate anions, IT-POP-1 possesses the highest surface area and the best CO 2 uptake capacity with excellent adsorption selectivity over N 2 . The roles of the task-specific components such as triazine, imidazolium, hydroxyl, and counter anions in CO 2 absorption and catalytic performance were illustrated. IT-POP-1 exhibits the highest catalytic activity and excellent recyclability in solvent- and additive-free cycloaddition reaction of CO 2 with epoxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiang; Shi, Hui; Kwak, Ja Hun

The hydrogenation of CO 2 was investigated over a wide range of reaction conditions, using two Pd/γ-Al 2O 3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (~11% and ~100%, respectively). Turnover rates for CO and CH 4 formation were both higher over 5% Pd/Al 2O 3 with a larger average Pd particle size than those over 0.5% Pd/Al 2O 3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al 2O 3 was higher by a factor of 2-3 than that on 0.5% Pd/Al 2O 3. The drastically different rate expressions and apparentmore » energies of activation for CO and CH 4 formation lead us to conclude that reverse water gas shift and CO 2 methanation do not share the same rate-limiting step on Pd, and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO 2 and H 2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO 2, H 2 and CO 2+H 2. The DRIFTS and MS results also demonstrate that no direct dissociation of CO 2 takes place over the two catalysts, and that CO 2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO 2 activation on the oxide support, and H 2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, while the other interacts more strongly with CO, which is mainly in multi-bound forms and remains stable in He flow at high temperatures, but is reactive towards adsorbed H atoms on Pd leading eventually to CH 4 formation. 5% Pd/Al 2O 3 contains a larger fraction of terrace sites favorable for forming these more stable CO species than 0.5% Pd/Al 2O 3. Consequently, we propose that the difference in the formation rate and selectivity to CH 4 on different Pd particle sizes stems from the different concentrations of the reactive intermediate for the methanation pathway on the Pd surface. JS gratefully acknowledges the financial support of this work by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.« less

Effect of open metal sites on adsorption of polar and nonpolar molecules in metal-organic framework Cu-BTC.

PubMed

Karra, Jagadeswara R; Walton, Krista S

2008-08-19

Atomistic grand canonical Monte Carlo simulations were performed in this work to investigate the role of open copper sites of Cu-BTC in affecting the separation of carbon monoxide from binary mixtures containing methane, nitrogen, or hydrogen. Mixtures containing 5%, 50%, or 95% CO were examined. The simulations show that electrostatic interactions between the CO dipole and the partial charges on the metal-organic framework (MOF) atoms dominate the adsorption mechanism. The binary simulations show that Cu-BTC is quite selective for CO over hydrogen and nitrogen for all three mixture compositions at 298 K. The removal of CO from a 5% mixture with methane is slightly enhanced by the electrostatic interactions of CO with the copper sites. However, the pore space of Cu-BTC is large enough to accommodate both molecules at their pure-component loadings, and in general, Cu-BTC exhibits no significant selectivity for CO over methane for the equimolar and 95% mixtures. On the basis of the pure-component and low-concentration behavior of CO, the results indicate that MOFs with open metal sites have the potential for enhancing adsorption separations of molecules of differing polarities, but the pore size relative to the sorbate size will also play a significant role.

Ionization-induced solvent migration in acetanilide-methanol clusters inferred from isomer-selective infrared spectroscopy.

PubMed

Weiler, Martin; Nakamura, Takashi; Sekiya, Hiroshi; Dopfer, Otto; Miyazaki, Mitsuhiko; Fujii, Masaaki

2012-12-07

We present the resonance-enhanced multiphoton ionization, infrared-ultraviolet hole burning (IR-UV HB), and IR dip spectra of the trans-acetanilide-methanol (AA-MeOH) cluster in the S(0), S(1), and cationic ground state (D(0)) in a supersonic jet. The IR-UV HB spectra demonstrate the co-existence of two isomers in S(0,1), in which MeOH binds either to the NH or the CO site of the peptide linkage in AA, denoted as AA(NH)-MeOH and AA(CO)-MeOH. When AA(CO)-MeOH is selectively ionized, its IR spectrum in D(0) is the same as that measured for AA(+) (NH)-MeOH. Thus, photoionization of AA(CO)-MeOH induces migration of MeOH from the CO to the NH site with 100% yield. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geochemical Impacts of Leaking CO2 from Subsurface Storage Reservoirs to Unconfined and Confined Aquifers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nikolla; Brown, Christopher F.; Wang, Guohui

2013-04-15

Experimental research work has been conducted and is undergoing at Pacific Northwest National Laboratory (PNNL) to address a variety of scientific issues related with the potential leaks of the carbon dioxide (CO2) gas from deep storage reservoirs. The main objectives of this work are as follows: • Develop a systematic understanding of how CO2 leakage is likely to influence pertinent geochemical processes (e.g., dissolution/precipitation, sorption/desorption and redox reactions) in the aquifer sediments. • Identify prevailing environmental conditions that would dictate one geochemical outcome over another. • Gather useful information to support site selection, risk assessment, policy-making, and public education effortsmore » associated with geological carbon sequestration. In this report, we present results from experiments conducted at PNNL to address research issues related to the main objectives of this effort. A series of batch and column experiments and solid phase characterization studies (quantitative x-ray diffraction and wet chemical extractions with a concentrated acid) were conducted with representative rocks and sediments from an unconfined, oxidizing carbonate aquifer, i.e., Edwards aquifer in Texas, and a confined aquifer, i.e., the High Plains aquifer in Kansas. These materials were exposed to a CO2 gas stream simulating CO2 gas leaking scenarios, and changes in aqueous phase pH and chemical composition were measured in liquid and effluent samples collected at pre-determined experimental times. Additional research to be conducted during the current fiscal year will further validate these results and will address other important remaining issues. Results from these experimental efforts will provide valuable insights for the development of site-specific, generation III reduced order models. In addition, results will initially serve as input parameters during model calibration runs and, ultimately, will be used to test model predictive capability and competency. The results from these investigations will provide useful information to support site selection, risk assessment, and public education efforts associated with geological, deep subsurface CO2 storage and sequestration.« less

Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

PubMed

Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

2017-09-19

As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none promote C-H bond formation. Thermochemical insights into the disparate reactivities of these clusters were achieved through hydricity measurements using SEC. We found that only [H-Fe 4 N(CO) 12 ] - and its derivative [H-Fe 4 N(CO) 11 (PPh 3 )] - have hydricities modest enough to avoid H 2 production but strong enough to make formate. [H-Fe 4 C(CO) 12 ] 2- is a stronger hydride donor, theoretically capable of making formate, but due to an overwhelming thermodynamic driving force and the increased electrostatic attraction between the more negative cluster and H + , only H 2 is observed experimentally. This illustrates the fundamental importance of controlling thermochemistry when designing new catalysts selective for C-H bond formation and establishes a hydricity range of 15.5-24.1 or 44-49 kcal mol -1 where C-H bond formation may be favored in water or MeCN, respectively.

Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

NASA Astrophysics Data System (ADS)

Maluangnont, Tosapol; Arsa, Pornanan; Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong; Gotoh, Kazuma; Sooknoi, Tawan

2016-06-01

While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K0.8Zn0.4Ti1.6O4 as an example. The low basicity (0.04 mmol CO2/g) and low desorption temperature (50-300 °C) shown by CO2- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO2. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.

Observations of Atmospheric Δ14CO2 at the Global and Regional Background Sites in China: Implication for Fossil Fuel CO2 Inputs.

PubMed

Niu, Zhenchuan; Zhou, Weijian; Cheng, Peng; Wu, Shugang; Lu, Xuefeng; Xiong, Xiaohu; Du, Hua; Fu, Yunchong

2016-11-15

Six months to more than one year of atmospheric Δ 14 CO 2 were measured in 2014-2015 at one global background site in Waliguan (WLG) and four regional background sites at Shangdianzi (SDZ), Lin'an (LAN), Longfengshan (LFS) and Luhuitou (LHT), China. The objectives of the study are to document the Δ 14 CO 2 levels at each site and to trace the variations in fossil fuel CO 2 (CO 2ff ) inputs at regional background sites. Δ 14 CO 2 at WLG varied from 7.1 ± 2.9‰ to 32.0 ± 3.2‰ (average 17.1 ± 6.8‰) in 2015, with high values generally in autumn/summer and low values in winter/spring. During the same period, Δ 14 CO 2 values at the regional background sites were found to be significantly (p < 0.05) lower than those at WLG, indicating different levels of CO 2ff inputs at those sites. CO 2ff concentrations at LAN (12.7 ± 9.6 ppm) and SDZ (11.5 ± 8.2 ppm) were significantly (p < 0.05) higher than those at LHT (4.6 ± 4.3 ppm) in 2015. There were no significant (p > 0.05) seasonal differences in CO 2ff concentrations for the regional sites. Regional sources contributed in part to the CO 2ff inputs at LAN and SDZ, while local sources dominated the trend observed at LHT. These data provide a preliminary understanding of atmospheric Δ 14 CO 2 and CO 2ff inputs for a range of Chinese background sites.

Well-Defined Models for the Elusive Dinuclear Intermediates of the Pauson-Khand Reaction.

PubMed

Hartline, Douglas R; Zeller, Matthias; Uyeda, Christopher

2016-05-10

The mechanism of the Pauson-Khand reaction has attracted significant interest due to the unusual dinuclear nature of the Co2 (CO)x active site. Experimental and computational data have indicated that the intermediates following the initial Co2 (CO)6 (alkyne) complex are thermodynamically unstable and do not build up in appreciable concentrations during the course of the reaction. As a consequence, the key steps that control the scope of viable substrates and various aspects of selectivity have remained largely uncharacterized. Herein, a direct experimental investigation of the dinuclear metallacycle-forming step of the Pauson-Khand reaction is reported. These studies capitalize on well-defined d(9) -d(9) dinickel complexes supported by a naphthyridine-diimine (NDI) pincer ligand as functional surrogates of Co2 (CO)8 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon Mineralization by Aqueous Precipitation for Beneficial Use of CO2 from Flue Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devenney, Martin; Gilliam, Ryan; Seeker, Randy

2013-08-01

The objective of this project is to demonstrate an innovative process to mineralize CO2 from flue gas directly to reactive carbonates and maximize the value and versatility of its beneficial use products. The program scope includes the design, construction, and testing of a CO2 Conversion to Material Products (CCMP) Pilot Demonstration Plant utilizing CO2 from the flue gas of a power production facility in Moss Landing, CA. This topical report covers Subphase 2a which is the design phase of pilot demonstration subsystems. Materials of construction have been selected and proven in both lab scale and prototype testing to be acceptablemore » for the reagent conditions of interest. The target application for the reactive carbonate material has been selected based upon small-scale feasibility studies and the design of a continuous fiber board production line has been completed. The electrochemical cell architecture and components have been selected based upon both lab scale and prototype testing. The appropriate quality control and diagnostic techniques have been developed and tested along with the required instrumentation and controls. Finally the demonstrate site infrastructure, NEPA categorical exclusion, and permitting is all ready for the construction and installation of the new units and upgrades.« less

Advances in Geological CO{sub 2} Sequestration and Co-Sequestration with O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verba, Circe A; O'Connor, William K.; Ideker, J.H.

2012-10-28

The injection of CO{sub 2} for Enhanced Oil Recovery (EOR) and sequestration in brine-bearing formations for long term storage has been in practice or under investigation in many locations globally. This study focused on the assessment of cement wellbore seal integrity in CO{sub 2}- and CO{sub 2}-O{sub 2}-saturated brine and supercritical CO{sub 2} environments. Brine chemistries (NaCl, MgCl{sub 2}, CaCl{sub 2}) at various saline concentrations were investigated at a pressure of 28.9 MPa (4200 psi) at both 50{degree}C and 85{degree}C. These parameters were selected to simulate downhole conditions at several potential CO{sub 2} injection sites in the United States. Classmore » H portland cement is not thermodynamically stable under these conditions and the formation of carbonic acid degrades the cement. Dissociation occurs and leaches cations, forming a CaCO{sub 3} buffered zone, amorphous silica, and other secondary minerals. Increased temperature affected the structure of C-S-H and the hydration of the cement leading to higher degradation rates.« less

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

PubMed

Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

2014-07-14

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

The effect of Fe-Rh alloying on CO hydrogenation to C 2+ oxygenates

DOE PAGES

Palomino, Robert; Magee, Joseph W.; Llorca, Jordi; ...

2015-05-20

A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO 2 catalysts for the synthesis of ethanol and other C 2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe–Rh alloys for catalyst with 1–7 wt% Fe and ~2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to ~4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburizationmore » as evidenced by the formation of small amounts of Fe 3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeO x also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe–Rh alloy phases. As a result, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed to the blocking or modifying of Rh active sites.« less

Analysis of flavin oxidation and electron-transfer inhibition in Plasmodium falciparum dihydroorotate dehydrogenase.

PubMed

Malmquist, Nicholas A; Gujjar, Ramesh; Rathod, Pradipsinh K; Phillips, Margaret A

2008-02-26

Plasmodium falciparum dihydroorotate dehydrogenase (pfDHODH) is a flavin-dependent mitochondrial enzyme that provides the only route to pyrimidine biosynthesis in the parasite. Clinically significant inhibitors of human DHODH (e.g., A77 1726) bind to a pocket on the opposite face of the flavin cofactor from dihydroorotate (DHO). This pocket demonstrates considerable sequence variability, which has allowed species-specific inhibitors of the malarial enzyme to be identified. Ubiquinone (CoQ), the physiological oxidant in the reaction, has been postulated to bind this site despite a lack of structural evidence. To more clearly define the residues involved in CoQ binding and catalysis, we undertook site-directed mutagenesis of seven residues in the structurally defined A77 1726 binding site, which we term the species-selective inhibitor site. Mutation of several of these residues (H185, F188, and F227) to Ala substantially decreased the affinity of pfDHODH-specific inhibitors (40-240-fold). In contrast, only a modest increase in the Kmapp for CoQ was observed, although mutation of Y528 in particular caused a substantial reduction in kcat (40-100-fold decrease). Pre-steady-state kinetic analysis by single wavelength stopped-flow spectroscopy showed that the mutations had no effect on the rate of the DHO-dependent reductive half-reaction, but most reduced the rate of the CoQ-dependent flavin oxidation step (3-20-fold decrease), while not significantly altering the Kdox for CoQ. As with the mutants, inhibitors that bind this site block the CoQ-dependent oxidative half-reaction without affecting the DHO-dependent step. These results identify residues involved in inhibitor binding and electron transfer to CoQ. Importantly, the data provide compelling evidence that the binding sites for CoQ and species-selective site inhibitors do not overlap, and they suggest instead that inhibitors act either by blocking the electron path between flavin and CoQ or by stabilizing a conformation that excludes CoQ binding.

The path to a successful one-million tonne demonstration of geological sequestration: Characterization, cooperation, and collaboration

USGS Publications Warehouse

Finley, R.J.; Greenberg, S.E.; Frailey, S.M.; Krapac, I.G.; Leetaru, H.E.; Marsteller, S.

2011-01-01

The development of the Illinois Basin-Decatur USA test site for a 1 million tonne injection of CO2 into the Mount Simon Sandstone saline reservoir beginning in 2011 has been a multiphase process requiring a wide array of personnel and resources that began in 2003. The process of regional characterization took two years as part of a Phase I effort focused on the entire Illinois Basin, located in Illinois, Indiana, and Kentucky, USA. Seeking the cooperation of an industrial source of CO2 and site selection within the Basin took place during Phase II while most of the concurrent research emphasis was on a set of small-scale tests of Enhanced Oil Recovery (EOR) and CO2 injection into a coal seam. Phase III began the commitment to the 1 million-tonne test site development through the collaboration of the Archer Daniels Midland Company (ADM) who is providing a site, the CO2, and developing a compression facility, of Schlumberger Carbon Services who is providing expertise for operations, drilling, geophysics, risk assessment, and reservoir modelling, and of the Illinois State Geological Survey (ISGS) whose geologists and engineers lead the Midwest Geological Sequestration Consortium (MGSC). Communications and outreach has been a collaborative effort of ADM, ISGS and Schlumberger Carbon Services. The Consortium is one of the seven Regional Carbon Sequestration Partnerships, a carbon sequestration research program supported by the National Energy Technology Laboratory of the U.S. Department of Energy. ?? 2011 Published by Elsevier Ltd.

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiol­ate and thio­ether donors: reactivity of an thiol­ate-bridged penta­nuclear Co2Ag3 complex with iodo­methane

PubMed Central

Fukuda, Yosuke; Yoshinari, Nobuto; Konno, Takumi

2017-01-01

Treatment of an S-bridged penta­nuclear AgI 3CoIII 2 complex, [Ag3{Co(L)}2]3+ [L 3– = N(CH2NHCH2CH2S−)3], in which two tris­(thiol­ate)-type mononuclear CoIII units ([Co(L)]) are bridged by three AgI ions through S atoms, with iodo­methane (CH3I) gave a new CoIII mononuclear complex, [Co(LMe2)]2+ [LMe2 − = N(CH2NHCH2CH2S−)(CH2NHCH2CH2SCH3)2], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF6 − anions to form the title compound, [Co(LMe2)](PF6)2. In the [Co(LMe2)]2+ cation, two of three thiol­ate groups in [Co(L)] are methyl­ated while one thiol­ate group remains unreacted. Although a total of eight stereoisomers are possible for [Co(LMe2)]2+, only a pair of enanti­omers {ΛRR- and ΔSS-[Co(LMe2)]2+} are selectively formed. In the crystal, the complex cations and the PF­6 − anions are connected through weak N—H⋯F, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional structure. Two F atoms in one PF6 anion are disordered over two sets of sites with refined occupancies of 0.61 (4) and 0.39 (4) and two F atoms in the other PF6 − anion are disordered over two sets of sites with occupancies of 0.5. PMID:28529774

Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons

PubMed Central

Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun; Vailionis, Arturas; Baricuatro, Jack H.; Higgins, Drew C.; Nitopi, Stephanie A.; Soriaga, Manuel P.; Jaramillo, Thomas F.

2017-01-01

In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the <100>, <111>, and <751> orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C–C coupling than Cu(111), Cu(751) is the most selective for >2e− oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction. PMID:28533377

Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

PubMed

Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

2017-06-01

Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Critical Review of the Impacts of Leaking CO 2 Gas and Brine on Groundwater Quality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nikolla; Zheng, Liange; Bacon, Diana H.

2015-09-30

Geological carbon sequestration (GCS) is a global carbon emission reduction strategy involving the capture of CO 2 emitted from fossil fuel burning power plants, as well as the subsequent injection of the captured CO 2 gas into deep saline aquifers or depleted oil and gas reservoirs. A critical question that arises from the proposed GCS is the potential impacts of CO 2 injection on the quality of drinking-water systems overlying CO 2 sequestration storage sites. Although storage reservoirs are evaluated and selected based on their ability to safely and securely store emplaced fluids, leakage of CO 2 from storage reservoirsmore » is a primary risk factor and potential barrier to the widespread acceptance of geologic CO 2 sequestration (OR Harvey et al. 2013; Y-S Jun et al. 2013; DOE 2007). Therefore, a systematic understanding of how CO 2 leakage would affect the geochemistry of potable aquifers, and subsequently control or affect elemental and contaminant release via sequential and/or simultaneous abiotic and biotic processes and reactions is vital.« less

Estimation of hydrocarbon biodegradation rates in gasoline-contaminated sediment from measured respiration rates

USGS Publications Warehouse

Baker, R.J.; Baehr, A.L.; Lahvis, M.A.

2000-01-01

An open microcosm method for quantifying microbial respiration and estimating biodegradation rates of hydrocarbons in gasoline-contaminated sediment samples has been developed and validated. Stainless-steel bioreactors are filled with soil or sediment samples, and the vapor-phase composition (concentrations of oxygen (O2), nitrogen (N2), carbon dioxide (CO2), and selected hydrocarbons) is monitored over time. Replacement gas is added as the vapor sample is taken, and selection of the replacement gas composition facilitates real-time decision-making regarding environmental conditions within the bioreactor. This capability allows for maintenance of field conditions over time, which is not possible in closed microcosms. Reaction rates of CO2 and O2 are calculated from the vapor-phase composition time series. Rates of hydrocarbon biodegradation are either measured directly from the hydrocarbon mass balance, or estimated from CO2 and O2 reaction rates and assumed reaction stoichiometries. Open microcosm experiments using sediments spiked with toluene and p-xylene were conducted to validate the stoichiometric assumptions. Respiration rates calculated from O2 consumption and from CO2 production provide estimates of toluene and p- xylene degradation rates within about ??50% of measured values when complete mineralization stoichiometry is assumed. Measured values ranged from 851.1 to 965.1 g m-3 year-1 for toluene, and 407.2-942.3 g m-3 year-1 for p- xylene. Contaminated sediment samples from a gasoline-spill site were used in a second set of microcosm experiments. Here, reaction rates of O2 and CO2 were measured and used to estimate hydrocarbon respiration rates. Total hydrocarbon reaction rates ranged from 49.0 g m-3 year-1 in uncontaminated (background) to 1040.4 g m-3 year-1 for highly contaminated sediment, based on CO2 production data. These rate estimates were similar to those obtained independently from in situ CO2 vertical gradient and flux determinations at the field site. In these experiments, aerobic conditions were maintained in the microcosms by using air as the replacement gas, thus preserving the ambient aerobic environment of the subsurface near the capillary zone. This would not be possible with closed microcosms.

Positive Darwinian Selection in the Piston That Powers Proton Pumps in Complex I of the Mitochondria of Pacific Salmon

PubMed Central

Garvin, Michael R.; Bielawski, Joseph P.; Gharrett, Anthony J.

2011-01-01

The mechanism of oxidative phosphorylation is well understood, but evolution of the proteins involved is not. We combined phylogenetic, genomic, and structural biology analyses to examine the evolution of twelve mitochondrial encoded proteins of closely related, yet phenotypically diverse, Pacific salmon. Two separate analyses identified the same seven positively selected sites in ND5. A strong signal was also detected at three sites of ND2. An energetic coupling analysis revealed several structures in the ND5 protein that may have co-evolved with the selected sites. These data implicate Complex I, specifically the piston arm of ND5 where it connects the proton pumps, as important in the evolution of Pacific salmon. Lastly, the lineage to Chinook experienced rapid evolution at the piston arm. PMID:21969854

Positive Darwinian selection in the piston that powers proton pumps in complex I of the mitochondria of Pacific salmon.

PubMed

Garvin, Michael R; Bielawski, Joseph P; Gharrett, Anthony J

2011-01-01

The mechanism of oxidative phosphorylation is well understood, but evolution of the proteins involved is not. We combined phylogenetic, genomic, and structural biology analyses to examine the evolution of twelve mitochondrial encoded proteins of closely related, yet phenotypically diverse, Pacific salmon. Two separate analyses identified the same seven positively selected sites in ND5. A strong signal was also detected at three sites of ND2. An energetic coupling analysis revealed several structures in the ND5 protein that may have co-evolved with the selected sites. These data implicate Complex I, specifically the piston arm of ND5 where it connects the proton pumps, as important in the evolution of Pacific salmon. Lastly, the lineage to Chinook experienced rapid evolution at the piston arm.

Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

NASA Astrophysics Data System (ADS)

Cadiau, Amandine; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant M.; Pillai, Renjith S.; Shkurenko, Aleksander; Martineau-Corcos, Charlotte; Maurin, Guillaume; Eddaoudi, Mohamed

2017-05-01

Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

Evaluating Potential for Large Releases from CO2 StorageReservoirs: Analogs, Scenarios, and Modeling Needs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Birkholzer, Jens; Pruess, Karsten; Lewicki, Jennifer

2005-09-19

While the purpose of geologic storage of CO{sub 2} in deep saline formations is to trap greenhouse gases underground, the potential exists for CO{sub 2} to escape from the target reservoir, migrate upward along permeable pathways, and discharge at the land surface. Such discharge is not necessarily a serious concern, as CO{sub 2} is a naturally abundant and relatively benign gas in low concentrations. However, there is a potential risk to health, safety and environment (HSE) in the event that large localized fluxes of CO{sub 2} were to occur at the land surface, especially where CO{sub 2} could accumulate. Inmore » this paper, we develop possible scenarios for large CO{sub 2} fluxes based on the analysis of natural analogues, where large releases of gas have been observed. We are particularly interested in scenarios which could generate sudden, possibly self-enhancing, or even eruptive release events. The probability for such events may be low, but the circumstances under which they might occur and potential consequences need to be evaluated in order to design appropriate site selection and risk management strategies. Numerical modeling of hypothetical test cases is needed to determine critical conditions for such events, to evaluate whether such conditions may be possible at designated storage sites, and, if applicable, to evaluate the potential HSE impacts of such events and design appropriate mitigation strategies.« less

Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei

Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevantmore » step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H-insertion steps in the aqueous phase, unlike those in the vapor phase, during the hydrogenation of acetic acid on Ru clusters.« less

Spectroscopic and Mechanistic Studies of Heterodimetallic Forms of Metallo-β-lactamase NDM-1

PubMed Central

2015-01-01

In an effort to characterize the roles of each metal ion in metallo-β-lactamase NDM-1, heterodimetallic analogues (CoCo-, ZnCo-, and CoCd-) of the enzyme were generated and characterized. UV–vis, 1H NMR, EPR, and EXAFS spectroscopies were used to confirm the fidelity of the metal substitutions, including the presence of a homogeneous, heterodimetallic cluster, with a single-atom bridge. This marks the first preparation of a metallo-β-lactamase selectively substituted with a paramagnetic metal ion, Co(II), either in the Zn1 (CoCd-NDM-1) or in the Zn2 site (ZnCo-NDM-1), as well as both (CoCo-NDM-1). We then used these metal-substituted forms of the enzyme to probe the reaction mechanism, using steady-state and stopped-flow kinetics, stopped-flow fluorescence, and rapid-freeze-quench EPR. Both metal sites show significant effects on the kinetic constants, and both paramagnetic variants (CoCd- and ZnCo-NDM-1) showed significant structural changes on reaction with substrate. These changes are discussed in terms of a minimal kinetic mechanism that incorporates all of the data. PMID:24754678

Theoretical study on the gas adsorption capacity and selectivity of CPM-200-In/Mg and CPM-200-In/Mg-X (-X = -NH2, -OH, -N, -F).

PubMed

Liu, Xiao-le; Chen, Guang-Hui; Wang, Xiu-Jun; Li, Peng; Song, Yi-Bing; Li, Rui-Yan

2017-11-15

The adsorption capacities of a heterometallic metal-organic framework (CPM-200-In/Mg) to VOCs (HCHO, C 2 H 4 , CH 4 , C 2 H 2 , C 3 H 8 , C 2 H 6 , C 2 H 3 Cl, C 2 H 2 Cl 2 , CH 2 Cl 2 and CHCl 3 ) and some inorganic gas molecules (HCN, SO 2 , NO, CO 2 , CO, H 2 S and NH 3 ), as well as its selectivity in ternary mixture systems of natural gas and post-combustion flue gas are theoretically explored at the grand canonical Monte Carlo (GCMC) and density functional theory (DFT) levels. It is shown that CPM-200-In/Mg is suitable for the adsorption of VOCs, particularly for HCHO (up to 0.39 g g -1 at 298 K and 1 bar), and the adsorption capacities of some inorganic gas molecules such as SO 2 , H 2 S and CO 2 match well with the sequence of their polarizability (SO 2 > H 2 S > CO 2 ). The large adsorption capacities of HCN and HCHO in the framework result from the strong interaction between adsorbates and metal centers, based on analyzing the radial distribution functions (RDF). Comparing C 2 H 4 and CH 4 molecules interacting with CPM-200-In/Mg by VDW interaction, we speculate that the high adsorption capacities of their chlorine derivatives in the framework could be due to the existence of halogen bonding or strong electrostatic and VDW interactions. It is found that the basic groups, including -NH 2 , -N and -OH, can effectively improve both the adsorption capacities and selectivity of CPM-200-In/Mg for harmful gases. Note that the adsorption capacity of CPM-200-In/Mg-NH 2 (site 2) (245 cm 3 g -1 ) for CO 2 exceeded that of MOF-74-Mg (228 cm 3 g -1 ) at 273 K and 1 bar and that for HCHO can reach 0.41 g g -1 , which is almost twice that of 438-MOF and nearly 45 times of that in active carbon. Moreover, for natural gas mixtures, the decarburization and desulfurization abilities of CPM-200-In/Mg-NH 2 (site 2) have exceeded those of the MOF-74 series, while for post-combustion flue gas mixtures, the desulfurization ability of CPM-200-In/Mg-NH 2 (site 2) is still comparable to those of the MOF-74 series at 303 K and 4 MPa. We hope that the current theoretical study could guide experimental research in the future.

Functionalized MIL-101 with imidazolium-based ionic liquids for the cycloaddition of CO2 and epoxides under mild condition

NASA Astrophysics Data System (ADS)

Liu, Dan; Li, Gang; Liu, Haiou

2018-01-01

A kind of multi-functional sites metal-organic framework (MOF) composite (MIL-101-IMBr) was successfully prepared by post-synthesis modification of MIL-101 with imidazolium-based ionic liquids. The ionic liquids not only functionalize as basic sites but also provide halide anions, which serve as a nucleophile in cycloaddition reaction. The prepared functional MOF materials were characterized by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, N2 adsorption-desorption and CO2 temperature programmed desorption. The results of fourier transform infrared spectroscopy and energy dispersive spectroscopy show that the MIL-101-IMBr composite was successfully synthesized. The N2 adsorption-desorption results clearly demonstrated that the modified composites still preserve high BET surface area and total pore volume. The composite exhibits high catalytic activity for the cycloaddition of CO2 with epoxides under mild and co-catalyst free conditions. The conversion of propylene oxide was 95.8% and the selectivity of cyclic carbonate was 97.6% under 0.8 MPa at 80 °C for 4 h. Moreover, the catalyst can be used for at least five times.

Analysis of the potential of near ground measurements of CO2 and CH4 in London, UK for the monitoring of city-scale emissions using an atmospheric transport model

NASA Astrophysics Data System (ADS)

Boon, A.; Broquet, G.; Clifford, D. J.; Chevallier, F.; Butterfield, D. M.; Pison, I.; Ramonet, M.; Paris, J. D.; Ciais, P.

2015-11-01

Carbon dioxide (CO2) and methane (CH4) mole fractions were measured at four near ground sites located in and around London during the summer of 2012 in view to investigate the potential of assimilating such measurements in an atmospheric inversion system for the monitoring of the CO2 and CH4 emissions in the London area. These data were analysed and compared with simulations using a modelling framework suited to building an inversion system: a 2 km horizontal resolution South of England configuration of the transport model CHIMERE driven by European Centre for Medium-Range Weather Forecasting (ECMWF) meteorological forcing, coupled to a 1 km horizontal resolution emission inventory (the UK National Atmospheric Emission Inventory). First comparisons reveal that local sources have a large impact on measurements and these local sources cannot be represented in the model at 2 km resolution. We evaluate methods to minimise some of the other critical sources of misfits between the observation data and the model simulation that overlap the signature of the errors in the emission inventory. These methods should make it easier to identify the corrections that should be applied to the inventory. Analysis is supported by observations from meteorological sites around the city and a three-week period of atmospheric mixing layer height estimations from lidar measurements. The difficulties of modelling the mixing layer depth and thus CO2 and CH4 concentrations during the night, morning and late afternoon led us to focus on the afternoon period for all further analyses. The misfits between observations and model simulations are high for both CO2 and CH4 (i.e., their root mean square (RMS) is between 8 and 12 parts per million (ppm) for CO2 and between 30 and 55 parts per billion (ppb) for CH4 at a given site). By analysing the gradients between the urban sites and a suburban or rural reference site, we are able to decrease the impact of uncertainties in the fluxes and transport outside the London area and in the model domain boundary conditions, and to better focus attention on the signature of London urban CO2 and CH4 emissions. This considerably improves the statistical agreement between the model and observations for CO2 (model-data RMS misfit of between 3 and 7 ppm) and to a lesser degree for CH4 (model-data RMS misfit of between 29 and 38 ppb). Between one of the urban sites and either reference site, selecting the gradients during periods wherein the reference site is upwind of the urban site further decreases the statistics of the misfits in general even though not systematically. In a final attempt to focus on the signature of the city anthropogenic emission in the mole fraction measurements, we use a theoretical ratio of gradients of CO to gradients of CO2 from fossil fuel emissions in the London area to diagnose observation based fossil fuel CO2 gradients, and compare them with the modelled ones. This estimate increases the consistency between the model and the measurements when considering one of the urban sites, but not when considering the other. While this study evaluates different approaches for increasing the consistency between the mesoscale model and the near ground data, and manages to decrease the random component of the analysed model data misfits to an extent that should not be prohibitive to extracting the signal from the London urban emissions, large biases remain in the final misfits. These biases are likely to be due to local emissions, to which the urban near ground sites are highly sensitive. This questions our current ability to exploit urban near ground data for the atmospheric inversion of city emissions based on models at spatial resolution coarser than 2 km.

A Restricted Boltzman Neural Net to Infer Carbon Uptake from OCO-2 Satellite Data

NASA Astrophysics Data System (ADS)

Halem, M.; Dorband, J. E.; Radov, A.; Barr-Dallas, M.; Gentine, P.

2015-12-01

For several decades, scientists have been using satellite observations to infer climate budgets of terrestrial carbon uptake employing inverse methods in conjunction with ecosystem models and coupled global climate models. This is an extremely important Big Data calculation today since the net annual photosynthetic carbon uptake changes annually over land and removes on average ~20% of the emissions from human contributions to atmospheric loading of CO2 from fossil fuels. Unfortunately, such calculations have large uncertainties validated with in-situ networks of measuring stations across the globe. One difficulty in using satellite data for these budget calculations is that the models need to assimilate surface fluxes of CO2 as well as soil moisture, vegatation cover and the eddy covariance of latent and sensible heat to calculate the carbon fixed in the soil while satellite spectral observations only provide near surface concentrations of CO2. In July 2014, NASA successfully launched OCO-2 which provides 3km surface measurements of CO2 over land and oceans. We have collected nearly one year of Level 2 XCO2 data from the OCO-2 satellite for 3 sites of ~200 km2 at equatorial, temperate and high latitudes. Each selected site was part of the Fluxnet or ARM system with tower stations for measuring and collecting CO2 fluxes on an hourly basis, in addition to eddy transports of the other parameters. We are also planning to acquire the 4km NDVI products from MODIS and registering the data to the 3km XCO2 footprints for the three sites. We have implemented a restricted Boltzman machine on the quantum annealing D-Wave computer, a novel deep learning neural net, to be used for training with station data to infer CO2 fluxes from collocated XCO2, MODIS vegetative land cover and MERRA reanalysis surface exchange products. We will present performance assessments of the D-Wave Boltzman machine for generating XCO2 fluxes from the OCO-2 satellite observations for the 3 sites by validating with monthly station flux data for one year as a potential assimilation input to the LIS model for obtaining the Net Ecosystem Exchange.

Preliminary clinical results of pulsed-dye laser therapy for recurrent respiratory papillomatosis

NASA Astrophysics Data System (ADS)

McMillan, Kathleen; Shapshay, Stanley M.; McGilligan, J. A.; Wang, Zhi; Rebeiz, Elie E.

1998-07-01

Recurrent respiratory papillomatosis (RRP) is a viral disease characterized by the growth of benign tumors on the vocal cords. Standard management of RRP currently consists of CO2 laser microsurgical ablation of the papillomas. Because of the recurrent nature of this disease, patients are often faced with significant cumulative risk of soft tissue complications such as vocal cord scarring. As a minimally traumatic alternative to management of RRP, we have investigated the use of the 585 nm pulsed dye laser (PDL) to cause regression of the papillomas by selective eradication of the tumor microvasculature. Three patients have been treated with the PDL at fluences of 6 J/cm2 (double pulses per irradiated site), 8 J/cm2 (single pulses), and 10 J/cm2 (single pulses), at noncritical areas within the larynx, using a specially designed micromanipulator. Lesions on the true cords were treated with the CO2 laser. Clinical examination showed that PDL treatment appeared to produce complete regression of papillomas. Unlike the sites of lesions treated by the CO2 laser, the epithelial surface at the PDL treatment sites was preserved intact. The presumed mechanism for papilloma regression following PDL treatment involves acute or chronic localized hypoxia caused by loss of tumor microvasculature.

Site differences in mild cognitive dysfunction (MCD) among patients with systemic lupus erythematosus (SLE).

PubMed

Kozora, E; Erkan, D; West, S G; Filley, C M; Zhang, L; Ramon, G; Duggan, E; Lockshin, M D

2013-01-01

Mild cognitive dysfunction (MCD) is common in patients with systemic lupus erythematosus (MCD-SLE) but few studies have investigated potential site differences. SLE patients from Denver, CO, and New York, NY, were enrolled in two different cognition studies employing similar screening methods. Using the resulting neuropsychological scores, cognitive impairment was calculated using a cognitive impairment index (CII). The rate of MCD-SLE was 24% at the Denver, CO, site and 60% at the New York, NY, site. The mean CII was 2.6 ± 2.3 versus 4.4 ± 2.7, respectively (p = 0.005). The NY participants had a significantly longer disease duration (p = 0.13) and higher American College of Rheumatology SLE criteria scores (p > 0.001). NY participants had a higher frequency of impairment in semantic verbal fluency (p = 0.005), visuomotor speed (p = 0.013), and motor sequencing (p = 0.001). A correlation was found between cognitive impairment and SLE disease duration (p = 0.03). The rate of MCD-SLE was greater in SLE patients from New York, NY, compared to patients in the Denver, CO, area. The greater duration of disease and higher prevalence of medical complications in the NY group might contribute to this difference. Findings suggest that MCD-SLE may differ by site, but future studies that better evaluate site or selection bias are recommended.

Reversible cobalt ion binding to imidazole-modified nanopipettes

PubMed Central

Sa, Niya; Fu, Yaqin; Baker, Lane A.

2010-01-01

In this report, we demonstrate that quartz nanopipettes modified with an imidazole-terminated silane respond to metal ions (Co2+) in solution. The response of nanopipettes is evaluated through examination of the ion current rectification response. By cycling nanopipettes between solutions of different pH, adsorbed Co2+ can be released from the nanopipette surface, to regenerate binding sites of the nanopipette. These results demonstrate that rectification-based sensing strategies for nanopore sensors can benefit from selection of recognition elements with intermediate binding affinities, such that reversible responses to be attained. PMID:21090777

Reversible cobalt ion binding to imidazole-modified nanopipettes.

PubMed

Sa, Niya; Fu, Yaqin; Baker, Lane A

2010-12-15

In this report, we demonstrate that quartz nanopipettes modified with an imidazole-terminated silane respond to metal ions (Co(2+)) in solution. The response of nanopipettes is evaluated through examination of the ion current rectification ratio. When nanopipettes are cycled between solutions of different pH, adsorbed Co(2+) can be released from the nanopipette surface, to regenerate binding sites of the nanopipette. These results demonstrate that rectification-based sensing strategies for nanopore sensors can benefit from selection of recognition elements with intermediate binding affinities, such that reversible responses can be attained.

An investigation of the presence of methane and other gases at the Uzundere-Izmir solid waste disposal site, Izmir, Turkey.

PubMed

Onargan, T; Kucuk, K; Polat, M

2003-01-01

Izmir is a large metropolitan city with a population of 3,114,860. The city consists of 27 townships, each township has a population of not less than 10,000 inhabitants. The two major solid waste disposal sites are in the townships of Uzundere and Harmandali. The amount of solid waste that is disposed at each of these sites is about 800 and 1800 t/day, respectively. In Uzundere, compost is produced from the organic fraction of urban solid wastes while the residual material is deposited at a disposal site with a remaining capacity of 700,000 m(3) as of 2001. Gas monitoring and measurements were carried out at the disposal site in Uzundere. For this purpose, nine sampling wells were drilled on selected locations. Each well was furnished with perforated metal pipes suitable for gas monitoring and measurements. The following gases were monitored: O(2), CH(4), CO, CO(2), and H(2)S. The most important finding was that the concentrations of CH(4) in the wells ranged from 7 to 57%. Dilution of the CH(4) by O(2) down to the LEL levels (5-15%) is always possible and poses a continuing risk at the site. Furthermore, the levels of O(2) require that access to the site be limited to only authorized personnel.

A pharmacophore model specific to active site of CYP1A2 with a novel molecular modeling explorer and CoMFA.

PubMed

Zhang, Tao; Wei, Dong-Qing; Chou, Kuo-Chen

2012-03-01

Comparative molecular field analysis (CoMFA) is a widely used 3D-QSAR method by which we can investigate the potential relation between biological activity of compounds and their structural features. In this study, a new application of this approach is presented by combining the molecular modeling with a new developed pharmacophore model specific to CYP1A2 active site. During constructing the model, we used the molecular dynamics simulation and molecular docking method to select the sensible binding conformations for 17 CYP1A2 substrates based on the experimental data. Subsequently, the results obtained via the alignment of binding conformations of substrates were projected onto the active- site residues, upon which a simple blueprint of active site was produced. It was validated by the experimental and computational results that the model did exhibit the high degree of rationality and provide useful insights into the substrate binding. It is anticipated that our approach can be extended to investigate the protein-ligand interactions for many other enzyme-catalyzed systems as well.

Metal-Free Carbon Materials for CO2 Electrochemical Reduction.

PubMed

Duan, Xiaochuan; Xu, Jiantie; Wei, Zengxi; Ma, Jianmin; Guo, Shaojun; Wang, Shuangyin; Liu, Huakun; Dou, Shixue

2017-11-01

The rapid increase of the CO 2 concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO 2 conversion, electrochemical reduction of CO 2 (CO 2 RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal-free electrocatalysts for the CO 2 RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high-temperature stability, and environmental friendliness. They exhibit remarkable CO 2 RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal-free catalysts for the CO 2 RR are highlighted. Recent advances regarding the identification of active sites for the CO 2 RR and the pathway of reduction of CO 2 to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom-doped carbon materials as metal-free electrocatalysts for the CO 2 RR are included. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anion mediated polytype selectivity among the basic salts of Co(II)

NASA Astrophysics Data System (ADS)

Ramesh, T. N.; Rajamathi, Michael; Vishnu Kamath, P.

2006-08-01

Basic salts of Co(II) crystallize in the rhombohedral structure. Two different polytypes, 3R 1 and 3R 2, with distinct stacking sequences of the metal hydroxide slabs, are possible within the rhombohedral structure. These polytypes are generated by simple translation of successive layers by (2/3, 1/3, z) or (1/3, 2/3, z). The symmetry of the anion and the mode of coordination influences polytype selection. Cobalt hydroxynitrate crystallizes in the structure of the 3R 2 polytype while the hydroxytartarate, hydroxychloride and α-cobalt hydroxide crystallize in the structure of the 3R 1 polytype. Cobalt hydroxysulfate is turbostratically disordered. The turbostratic disorder is a direct consequence of the mismatch between the crystallographically defined interlayer sites generated within the crystal and the tetrahedral symmetry of the SO 42- ions.

Superfund Record of Decision (EPA Region 7): Bee Cee Manufacturing Co., Malden, MO, September 30, 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

This decision document presents the remedial action selected to cleanup groundwater contaminant at the Bee Cee Manufacturing site in Malden, Missouri. The remedy selected to remediate contaminated groundwater at the Bee Cee Manufacturing site is natural attenuation, groundwater monitoring and institutional controls.

Plant-plant interactions mediate the plastic and genotypic response of Plantago asiatica to CO2: an experiment with plant populations from naturally high CO2 areas.

PubMed

van Loon, Marloes P; Rietkerk, Max; Dekker, Stefan C; Hikosaka, Kouki; Ueda, Miki U; Anten, Niels P R

2016-06-01

The rising atmospheric CO2 concentration ([CO2]) is a ubiquitous selective force that may strongly impact species distribution and vegetation functioning. Plant-plant interactions could mediate the trajectory of vegetation responses to elevated [CO2], because some plants may benefit more from [CO2] elevation than others. The relative contribution of plastic (within the plant's lifetime) and genotypic (over several generations) responses to elevated [CO2] on plant performance was investigated and how these patterns are modified by plant-plant interactions was analysed. Plantago asiatica seeds originating from natural CO2 springs and from ambient [CO2] sites were grown in mono stands of each one of the two origins as well as mixtures of both origins. In total, 1944 plants were grown in [CO2]-controlled walk-in climate rooms, under a [CO2] of 270, 450 and 750 ppm. A model was used for upscaling from leaf to whole-plant photosynthesis and for quantifying the influence of plastic and genotypic responses. It was shown that changes in canopy photosynthesis, specific leaf area (SLA) and stomatal conductance in response to changes in growth [CO2] were mainly determined by plastic and not by genotypic responses. We further found that plants originating from high [CO2] habitats performed better in terms of whole-plant photosynthesis, biomass and leaf area, than those from ambient [CO2] habitats at elevated [CO2] only when both genotypes competed. Similarly, plants from ambient [CO2] habitats performed better at low [CO2], also only when both genotypes competed. No difference in performance was found in mono stands. The results indicate that natural selection under increasing [CO2] will be mainly driven by competitive interactions. This supports the notion that plant-plant interactions have an important influence on future vegetation functioning and species distribution. Furthermore, plant performance was mainly driven by plastic and not by genotypic responses to changes in atmospheric [CO2]. © The Author 2016. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Plant–plant interactions mediate the plastic and genotypic response of Plantago asiatica to CO2: an experiment with plant populations from naturally high CO2 areas

PubMed Central

van Loon, Marloes P.; Rietkerk, Max; Dekker, Stefan C.; Hikosaka, Kouki; Ueda, Miki U.; Anten, Niels P. R.

2016-01-01

Background and Aims The rising atmospheric CO2 concentration ([CO2]) is a ubiquitous selective force that may strongly impact species distribution and vegetation functioning. Plant–plant interactions could mediate the trajectory of vegetation responses to elevated [CO2], because some plants may benefit more from [CO2] elevation than others. The relative contribution of plastic (within the plant’s lifetime) and genotypic (over several generations) responses to elevated [CO2] on plant performance was investigated and how these patterns are modified by plant–plant interactions was analysed. Methods Plantago asiatica seeds originating from natural CO2 springs and from ambient [CO2] sites were grown in mono stands of each one of the two origins as well as mixtures of both origins. In total, 1944 plants were grown in [CO2]-controlled walk-in climate rooms, under a [CO2] of 270, 450 and 750 ppm. A model was used for upscaling from leaf to whole-plant photosynthesis and for quantifying the influence of plastic and genotypic responses. Key Results It was shown that changes in canopy photosynthesis, specific leaf area (SLA) and stomatal conductance in response to changes in growth [CO2] were mainly determined by plastic and not by genotypic responses. We further found that plants originating from high [CO2] habitats performed better in terms of whole-plant photosynthesis, biomass and leaf area, than those from ambient [CO2] habitats at elevated [CO2] only when both genotypes competed. Similarly, plants from ambient [CO2] habitats performed better at low [CO2], also only when both genotypes competed. No difference in performance was found in mono stands. Conclusion The results indicate that natural selection under increasing [CO2] will be mainly driven by competitive interactions. This supports the notion that plant–plant interactions have an important influence on future vegetation functioning and species distribution. Furthermore, plant performance was mainly driven by plastic and not by genotypic responses to changes in atmospheric [CO2]. PMID:27192707

Regional-scale brine migration along vertical pathways due to CO2 injection - Part 1: The participatory modeling approach

NASA Astrophysics Data System (ADS)

Scheer, Dirk; Konrad, Wilfried; Class, Holger; Kissinger, Alexander; Knopf, Stefan; Noack, Vera

2017-06-01

Saltwater intrusion into potential drinking water aquifers due to the injection of CO2 into deep saline aquifers is one of the potential hazards associated with the geological storage of CO2. Thus, in a site selection process, models for predicting the fate of the displaced brine are required, for example, for a risk assessment or the optimization of pressure management concepts. From the very beginning, this research on brine migration aimed at involving expert and stakeholder knowledge and assessment in simulating the impacts of injecting CO2 into deep saline aquifers by means of a participatory modeling process. The involvement exercise made use of two approaches. First, guideline-based interviews were carried out, aiming at eliciting expert and stakeholder knowledge and assessments of geological structures and mechanisms affecting CO2-induced brine migration. Second, a stakeholder workshop including the World Café format yielded evaluations and judgments of the numerical modeling approach, scenario selection, and preliminary simulation results. The participatory modeling approach gained several results covering brine migration in general, the geological model sketch, scenario development, and the review of the preliminary simulation results. These results were included in revised versions of both the geological model and the numerical model, helping to improve the analysis of regional-scale brine migration along vertical pathways due to CO2 injection.

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst

PubMed Central

2016-01-01

Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni–Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources. PMID:27610415

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst.

PubMed

Dai, Lei; Qin, Qing; Zhao, Xiaojing; Xu, Chaofa; Hu, Chengyi; Mo, Shiguang; Wang, Yu Olivia; Lin, Shuichao; Tang, Zichao; Zheng, Nanfeng

2016-08-24

Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni-Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources.

Support Effects in Catalysis Studied by in-situ Sum Frequency Generation Vibrational Spectroscopy and in-situ X-Ray Spectroscopies

NASA Astrophysics Data System (ADS)

Kennedy, Griffin John

Kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst. In order to establish a paradigm for metal-support interactions using colloidally synthesized Pt nanoparticles the ability of the organic capping agent to inhibit reactivity and interaction with the support must first be assessed. Pt nanoparticles capped by poly(vinylpyrrolidone) (PVP), and those from which the PVP is removed by UV light exposure, are investigated for two reactions, the hydrogenation of ethylene and the oxidation of methanol. It is shown that prior to PVP removal the particles are moderately active for both reactions. Following removal, the activity for the two reactions diverges, the ethylene hydrogenation rate increases 10-fold, while the methanol oxidation rate decreases 3-fold. To better understand this effect the capping agent prior to, and the residual carbon remaining after UV treatment are probed by sum frequency generation vibrational spectroscopy. Prior to removal no major differences are observed when the particles are exposed to alternating H2 and O2 environments. When the PVP is removed, carbonaceous fragments remain on the surface that dynamically restructure in H2 and O2. These fragments create a tightly bound shell in an oxygen environment and a porous coating of hydrogenated carbon in the hydrogen environment. Reaction rate measurements of thermally cleaned PVP and oleic acid capped particles show this effect to be independent of cleaning method or capping agent. In all this demonstrates the ability of the capping agent to mediate nanoparticle catalysis. With this established the hydrogenation of furfural by Pt supported on SiO2 and TiO2 was investigated by an approach combining reaction studies with SFG in order to gain molecular level insight into the nature of the metal-support interaction. This is the first instance of SFG being used to probe the factors governing selectivity in a supported catalyst system. This work revealed that TiO2 possessed sites that, while inactive without Pt, became highly active for the selective conversion of furfural to furfuryl alcohol. By SFG a TiO2 bound intermediate species was identified that could explain the highly selective nature of the reaction by Pt/TiO2. In combination with density functional theory calculations it was determined that furfural bound favorably to oxygen vacancy sites on the TiO2 surface through the aldehyde oxygen, which in turn activated the aldehyde group for hydrogenation by a charge transfer mechanism. This intermediate could then react with spillover hydrogen from the Pt surface to form furfuryl alcohol. In an effort to generalize this mechanism to additional molecules and reducible oxides the work was expanded to the hydrogenation of crotonaldehyde with cobalt oxide as an additional support. Reaction studies and SFG study of the Pt/TiO2, Pt/Co3O4, and Pt/SiO 2 catalysts, revealed a reaction pathway for Pt/TiO2 and Pt/Co3O4 which selectively produced alcohol products, crotyl alcohol and butanol, while no alcohol production was observed for the Pt/SiO2 catalyst. A thorough study of the possible secondary reaction pathways revealed that butanol was formed in a concerted manner, rather than through sequential hydrogenation of the C=C and C=O groups. Sum frequency generation studies revealed that Pt supported on SiO2 yielded identical reaction intermediates as Pt single crystals, further cementing the passive role of SiO2. Spectra obtained from the cobalt and titanium oxide supported catalysts revealed adsorption sites exist on the oxide surfaces through which the molecule binds via the aldehyde group. These sites are believed to be the active sites for alcohol production. In the case of Co3O 4 ambient pressure x-ray photoelectron spectroscopy and x-ray absorption spectroscopy reveal a reduction of the oxide surface under reaction conditions indicating the adsorption sites on the oxide exist on a reduced surface, additional evidence for the site being an O-vacancy. Lastly a before undiscovered example of encapsulation of a metal particle by an oxide support is observed for the Pt/Co3O4 system by ambient pressure x-ray photoelectron spectroscopy. Under mild conditions an encapsulated state is reached in which the oxide covers the Pt surface, yet does not inhibit reactivity. In fact the total activity of the catalyst increases dramatically and a change in product selectivity was observed. (Abstract shortened by ProQuest.).

Design of electrolyzer for carbon dioxide conversion to fuels and chemicals

NASA Astrophysics Data System (ADS)

Rosen, Jonathan S.

The stabilization of global atmospheric CO2 levels requires a transition towards a renewable energy based economy as well as methods for handling current CO2 output from fossil fuels. Challenges with renewable energy intermittency have thus far limited the use of these alternative energy sources to only a fraction of the current energy portfolio. To enable more widespread use of renewable energy systems, methods of large scale energy storage must be developed to store excess renewable energy when demand is low and allow for combined use of energy storage and renewable systems when demand is high. To date, no one technique has demonstrated energy storage methods on the gigawatt scale needed for integration with renewable sources; therefore the development of suitable energy storage technologies, such as CO2 electrolysis to fuels is needed. In this work, research efforts have focused on two major thrusts related to electrochemical methods of CO 2 conversion to fuels. The first thrust focuses on the synthesis and design of highly efficient anode and cathode catalysts with emphasis on understanding structure-property relationships. A second thrust focuses on the design of novel electrochemical devices for CO2 conversion and integration of synthesized materials into flow cell systems. On the anode side, the synthesis of highly active catalysts using abundant transition metals is crucial to reducing capital costs and enabling widespread use of electrochemical CO2 conversion devices. Highly active mesoporous Co3O4 and metal-substituted Co3O4 water oxidation catalysts were designed to investigate the role of the spinel structure on water oxidation activity. Further analysis of metal substituted samples reveal the importance of the octahedral sites in the spinel structure, which was later used to design an Mg-Co3O4 sample with improved water oxidation activity. The design of efficient cathode materials which can selectivity reduce CO2 to fuels and chemicals is critical to the widespread use of CO2 electrolysis. A nanoporous Ag material was synthesized through a dealloying technique able to operate with less than 0.5 V overpotential and high selectivity towards CO. CO is a valuable intermediate chemical which can used in Fischer-Tropsch or Gas-to-liquids technologies to produce liquids fuels. A detailed investigation of nanostructured Ag catalysts found stepped sites to be responsible for enhanced CO2 reduction activity due to improved stabilization of the COOH intermediate on the catalyst surface. In addition, an low-cost Zn dendrite electrocatalyst was developed using an electroplating technique. Low coordinated sites formed through electrodeposition demonstrated the suppression of hydrogen evolution while maintaining CO activity. The Zn dendrite electrocatalyst was further examined using a newly developed in situ X-ray absorption technique able to probe catalyst stability and crystalline structure under CO2 reduction operating conditions. A final hurdle in the realization of CO2 electrolysis technologies is the integration of catalysts into working flow cell devices. To address this issue and enable testing in a practical system, a highly efficient and robust CO2 electrolysis flow cell was designed including the scale up of the previous nanoporous Ag synthesis procedure. Using the modified porous Ag catalyst, currents in the Amp regime were demonstrated approaching rates needed for energy storage applications. Stability on the order of days was successfully demonstrated due to use of robust system components and conditions suitable for process scale up.

Greenhouse gas measurements from a UK network of tall towers: technical description and first results

NASA Astrophysics Data System (ADS)

Stanley, Kieran M.; Grant, Aoife; O'Doherty, Simon; Young, Dickon; Manning, Alistair J.; Stavert, Ann R.; Spain, T. Gerard; Salameh, Peter K.; Harth, Christina M.; Simmonds, Peter G.; Sturges, William T.; Oram, David E.; Derwent, Richard G.

2018-03-01

A network of three tall tower measurement stations was set up in 2012 across the United Kingdom to expand measurements made at the long-term background northern hemispheric site, Mace Head, Ireland. Reliable and precise in situ greenhouse gas (GHG) analysis systems were developed and deployed at three sites in the UK with automated instrumentation measuring a suite of GHGs. The UK Deriving Emissions linked to Climate Change (UK DECC) network uses tall (165-230 m) open-lattice telecommunications towers, which provide a convenient platform for boundary layer trace gas sampling. In this paper we describe the automated measurement system and first results from the UK DECC network for CO2, CH4, N2O, SF6, CO and H2. CO2 and CH4 are measured at all of the UK DECC sites by cavity ring-down spectroscopy (CRDS) with multiple inlet heights at two of the three tall tower sites to assess for boundary layer stratification. The short-term precisions (1σ on 1 min means) of CRDS measurements at background mole fractions for January 2012 to September 2015 is < 0.05 µmol mol-1 for CO2 and < 0.3 nmol mol-1 for CH4. Repeatability of standard injections (1σ) is < 0.03 µmol mol-1 for CO2 and < 0.3 nmol mol-1 for CH4 for the same time period. N2O and SF6 are measured at three of the sites, and CO and H2 measurements are made at two of the sites, from a single inlet height using gas chromatography (GC) with an electron capture detector (ECD), flame ionisation detector (FID) or reduction gas analyser (RGA). Repeatability of individual injections (1σ) on GC and RGA instruments between January 2012 and September 2015 for CH4, N2O, SF6, CO and H2 measurements were < 2.8 nmol mol-1, < 0.4 nmol mol-1, < 0.07 pmol mol-1, < 2 nmol mol-1 and < 3 nmol mol-1, respectively. Instrumentation in the network is fully automated and includes sensors for measuring a variety of instrumental parameters such as flow, pressures, and sampling temperatures. Automated alerts are generated and emailed to site operators when instrumental parameters are not within defined set ranges. Automated instrument shutdowns occur for critical errors such as carrier gas flow rate deviations. Results from the network give good spatial and temporal coverage of atmospheric mixing ratios within the UK since early 2012. Results also show that all measured GHGs are increasing in mole fraction over the selected reporting period and, except for SF6, exhibit a seasonal trend. CO2 and CH4 also show strong diurnal cycles, with night-time maxima and daytime minima in mole fractions.

Ground deformation monitoring using RADARSAT-2 DInSAR-MSBAS at the Aquistore CO2 storage site in Saskatchewan (Canada)

NASA Astrophysics Data System (ADS)

Czarnogorska, M.; Samsonov, S.; White, D.

2014-11-01

The research objectives of the Aquistore CO2 storage project are to design, adapt, and test non-seismic monitoring methods for measurement, and verification of CO2 storage, and to integrate data to determine subsurface fluid distributions, pressure changes and associated surface deformation. Aquistore site is located near Estevan in Southern Saskatchewan on the South flank of the Souris River and west of the Boundary Dam Power Station and the historical part of Estevan coal mine in southeastern Saskatchewan, Canada. Several monitoring techniques were employed in the study area including advanced satellite Differential Interferometric Synthetic Aperture Radar (DInSAR) technique, GPS, tiltmeters and piezometers. The targeted CO2 injection zones are within the Winnipeg and Deadwood formations located at > 3000 m depth. An array of monitoring techniques was employed in the study area including advanced satellite Differential Interferometric Synthetic Aperture Radar (DInSAR) with established corner reflectors, GPS, tiltmeters and piezometers stations. We used airborne LIDAR data for topographic phase estimation, and DInSAR product geocoding. Ground deformation maps have been calculated using Multidimensional Small Baseline Subset (MSBAS) methodology from 134 RADARSAT-2 images, from five different beams, acquired during 20120612-20140706. We computed and interpreted nine time series for selected places. MSBAS results indicate slow ground deformation up to 1 cm/year not related to CO2 injection but caused by various natural and anthropogenic causes.

Grassland productivity limited by multiple nutrients.

PubMed

Fay, Philip A; Prober, Suzanne M; Harpole, W Stanley; Knops, Johannes M H; Bakker, Jonathan D; Borer, Elizabeth T; Lind, Eric M; MacDougall, Andrew S; Seabloom, Eric W; Wragg, Peter D; Adler, Peter B; Blumenthal, Dana M; Buckley, Yvonne M; Chu, Chengjin; Cleland, Elsa E; Collins, Scott L; Davies, Kendi F; Du, Guozhen; Feng, Xiaohui; Firn, Jennifer; Gruner, Daniel S; Hagenah, Nicole; Hautier, Yann; Heckman, Robert W; Jin, Virginia L; Kirkman, Kevin P; Klein, Julia; Ladwig, Laura M; Li, Qi; McCulley, Rebecca L; Melbourne, Brett A; Mitchell, Charles E; Moore, Joslin L; Morgan, John W; Risch, Anita C; Schütz, Martin; Stevens, Carly J; Wedin, David A; Yang, Louie H

2015-07-06

Terrestrial ecosystem productivity is widely accepted to be nutrient limited(1). Although nitrogen (N) is deemed a key determinant of aboveground net primary production (ANPP)(2,3), the prevalence of co-limitation by N and phosphorus (P) is increasingly recognized(4-8). However, the extent to which terrestrial productivity is co-limited by nutrients other than N and P has remained unclear. Here, we report results from a standardized factorial nutrient addition experiment, in which we added N, P and potassium (K) combined with a selection of micronutrients (K+μ), alone or in concert, to 42 grassland sites spanning five continents, and monitored ANPP. Nutrient availability limited productivity at 31 of the 42 grassland sites. And pairwise combinations of N, P, and K+μ co-limited ANPP at 29 of the sites. Nitrogen limitation peaked in cool, high latitude sites. Our findings highlight the importance of less studied nutrients, such as K and micronutrients, for grassland productivity, and point to significant variations in the type and degree of nutrient limitation. We suggest that multiple-nutrient constraints must be considered when assessing the ecosystem-scale consequences of nutrient enrichment.

Enhanced down regulation of cortical +-propranolol sensitive ( sup 3 H)-DHA binding sites by co-administration of DMI and 5-HT sub 1A partial agonist gepirone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geissler, M.A.; Yocca, F.D.

1990-02-26

The putative interrelationship between the noradrenergic and serotonergic systems has been supported by numerous studies. Recently, Dudley et al. (1989) demonstrated significant down regulation of cortical {beta}-adrenergic receptors by co-administration of desipramine (DMI), a norepinephrine uptake inhibitor, and the full 5-HT{sub 1A} agonist 8-OH-DPAT. To this end, the effects of acute and chronic (4 and 14 day) administration of DMI, gepirone, a selective 5-HT{sub 1A} post-synaptic partial agonist, as well as a combination of the two, on cortical ({plus minus})-propranolol sensitive ({sup 3}H)-DHA binding sites were examined in rats. Down regulation was apparent after 4 and 14 day treatment withmore » DMI. However, this was not the case with gepirone. Of particular importance is the demonstration of a greater magnitude of down regulation with co-administration of a greater magnitude of down regulation with co-administration of DMI and gepirone. These results suggests that alteration in rat cortical ({plus minus})-propranolol sensitive ({sup 3}H)-DHA binding sites by noradrenergic uptake inhibitors can be further modulated by selective partial agonist activity at central 5-HT{sub 1A} postsynaptic receptors. Further data on the co-administration of DMI and BMY 7378 (7,9-dioxo-8-(2-(4-{und o}-methoxyphenylpiperazinyl)ethyl)-8-azaspiro(4,5)decane dihydrochloride), a weak partial agonist at postsynaptic 5-HT{sub 1A} receptors, are also presented.« less

Rational design of a low-cost, high-performance metal–organic framework for hydrogen storage and carbon capture

DOE PAGES

Witman, Matthew; Ling, Sanliang; Gladysiak, Andrzej; ...

2016-12-16

Here, we present the in silico design of a MOF-74 analogue, hereon known as M 2(DHFUMA) [M = Mg, Fe, Co, Ni, Zn], with enhanced small-molecule adsorption properties over the original M 2(DOBDC) series. Constructed from 2,3-dihydroxyfumarate (DHFUMA), an aliphatic ligand which is smaller than the aromatic 2,5-dioxidobenzene-1,4-dicarboxylate (DOBDC), the M 2(DHFUMA) framework has a reduced channel diameter, resulting in higher volumetric density of open metal sites and significantly improved volumetric hydrogen (H 2) storage potential. Furthermore, the reduced distance between two adjacent open metal sites in the pore channel leads to a CO 2 binding mode of one moleculemore » per two adjacent metals with markedly stronger binding energetics. Through dispersion-corrected density functional theory (DFT) calculations of guest–framework interactions and classical simulation of the adsorption behavior of binary CO 2:H 2O mixtures, we theoretically predict the M 2(DHFUMA) series as an improved alternative for carbon capture over the M 2(DOBDC) series when adsorbing from wet flue gas streams. The improved CO 2 uptake and humidity tolerance in our simulations is tunable based upon metal selection and adsorption temperature which, combined with the significantly reduced ligand expense, elevates this material’s potential for CO 2 capture and H 2 storage. The dynamical and elastic stabilities of Mg 2(DHFUMA) were verified by hybrid DFT calculations, demonstrating its significant potential for experimental synthesis.« less

Rational Design of a Low-Cost, High-Performance Metal–Organic Framework for Hydrogen Storage and Carbon Capture

PubMed Central

2016-01-01

We present the in silico design of a MOF-74 analogue, hereon known as M2(DHFUMA) [M = Mg, Fe, Co, Ni, Zn], with enhanced small-molecule adsorption properties over the original M2(DOBDC) series. Constructed from 2,3-dihydroxyfumarate (DHFUMA), an aliphatic ligand which is smaller than the aromatic 2,5-dioxidobenzene-1,4-dicarboxylate (DOBDC), the M2(DHFUMA) framework has a reduced channel diameter, resulting in higher volumetric density of open metal sites and significantly improved volumetric hydrogen (H2) storage potential. Furthermore, the reduced distance between two adjacent open metal sites in the pore channel leads to a CO2 binding mode of one molecule per two adjacent metals with markedly stronger binding energetics. Through dispersion-corrected density functional theory (DFT) calculations of guest–framework interactions and classical simulation of the adsorption behavior of binary CO2:H2O mixtures, we theoretically predict the M2(DHFUMA) series as an improved alternative for carbon capture over the M2(DOBDC) series when adsorbing from wet flue gas streams. The improved CO2 uptake and humidity tolerance in our simulations is tunable based upon metal selection and adsorption temperature which, combined with the significantly reduced ligand expense, elevates this material’s potential for CO2 capture and H2 storage. The dynamical and elastic stabilities of Mg2(DHFUMA) were verified by hybrid DFT calculations, demonstrating its significant potential for experimental synthesis. PMID:28127415

Fluoride-selective colorimetric sensor based on thiourea binding site and anthraquinone reporter.

PubMed

Wu, Fang-ying; Hu, Mei-hua; Wu, Yu-mei; Tan, Xiao-fang; Zhao, Yong-qiang; Ji, Zhao-jun

2006-11-01

A structurally simple colorimetric sensor, N-4-nitrobenzene-N'-1'-anthraquinone-thiourea (1), for anions was synthesized and characterized by (1)H NMR, ESI mass and IR methods. In acetonitrile, the addition of F(-) changed 1 solution from colorless to yellow. In the presence of other anions such as CH(3)CO(2)(-), H(2)PO(4)(-), HSO(4)(-) and Cl(-), however, the absorption spectrum of 1 was slightly red shifted with no obvious color changes observed. The association constants of anionic complexes followed the order of F(-)>CH(3)CO(2)(-)>H(2)PO(4)(-)>HSO(4)(-)>Cl(-)>Br(-), which was different from the order of anion basicity. AM1 calculation results indicated that the most stable configuration of 1 existed in the Z-E-conformation with a six-membered ring via intramolecular hydrogen bond. This made thiourea moiety of 1 in an unfavorable conformation to bond with oxygen-anionic substrates such as CH(3)CO(2)(-) and H(2)PO(4)(-), thus leading to a high selectivity and sensitivity for the detection of F(-).

Site occupancy trend of Co in Ni{sub 2}MnIn: Ab initio approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pal, Soumyadipta, E-mail: soumyadipta.pal@gmail.com; Mahadevan, Priya; Biswas, C.

2015-06-24

The trend of site occupation of Co at Ni sites of Ni{sub 2}MnIn system is studied in austenitic phase having L2{sub 1} structure by ab initio density functional theory (DFT) calculation. The Co atoms prefer to be at Ni sites rather than Mn site and are ferromagetically coupled with Ni and Mn. The ground state has tetragonal structure for Ni{sub 1.5}Co{sub 0.5}MnIn and Ni{sub 1.25}Co{sub 0.75}MnIn. The Co tends to form cluster.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venteris, Erik R.; Skaggs, Richard; Wigmosta, Mark S.

The warm sunny climate and unoccupied arid lands in the American southwest are favorable factors for algae cultivation. However, additional resources affect the overall viability of specific sites and regions. We investigated the tradeoffs between growth rate, water, and CO 2 availability and costs for two strains: N. salina and Chlorella sp. We conducted site selection exercises (~88,000 US sites) to produce 21 billion gallons yr -1 (BGY) of renewable diesel (RD). Experimental trials from the National Alliance for Advanced Biofuels and Bio-Products (NAABB) team informed the growth model of our Biomass Assessment Tool (BAT). We simulated RD production bymore » both lipid extraction and hydrothermal liquefaction. Sites were prioritized by the net value of biofuel minus water and flue gas costs. Water cost models for N. salina were based on seawater and high salinity groundwater and for Chlorella, fresh and brackish groundwater. CO 2 costs were based on a flue gas delivery model. Selections constrained by production and water were concentrated along the Gulf of Mexico and southeast Atlantic coasts due to high growth rates and low water costs. Adding flue gas constraints increased the spatial distribution, but the majority of sites remained in the southeast. The 21 BGY target required ~3.8 million hectares of mainly forest (41.3%) and pasture (35.7%). Exclusion in favor of barren and scrub lands forced most production to the southwestern US, but with increased water consumption (5.7 times) and decreased economic efficiency (-38%).« less

Significant enhancement of gas uptake capacity and selectivity via the judicious increase of open metal sites and Lewis basic sites within two polyhedron-based metal-organic frameworks.

PubMed

Liu, Bing; Yao, Shuo; Shi, Chao; Li, Guanghua; Huo, Qisheng; Liu, Yunling

2016-02-21

Two new isomorphous polyhedron-based MOFs ( and ), with dual functionalities of OMSs and LBSs, have been synthesized by using the SBB strategy. By judiciously avoiding the DABCO axial ligand, possesses more OMSs than , and exhibits a significant enhancement of CO2 uptake capacity 210 versus 162 cm(3) g(-1) for at 273 K under 1 bar.

Strategic use of the underground for an energy mix plan, synergies among CO2 and CH4 Geological Storage and Geothermal Energy: Italian Energy review and Latium case study

NASA Astrophysics Data System (ADS)

Procesi, M.; Cantucci, B.; Buttinelli, M.; Armezzani, G.; Quattrocchi, F.

2012-04-01

Since the world-wide energy demand has been growing so much in the last years, it is necessary to develop a strategic mix-energy plan to supply low GHG (GreenHouseGas) emissions energy and solve the problem of CO2 emission increasing. A recent study published by European Commission shows that, if existing trends continue, by 2050 CO2 emissions will be unsustainably high: 900-1000 parts per million by volume. The European Commission in 2007 underline the necessity to elaborate, at European level, a Strategic Energy Technology Plan focused on non-carbon or reduced-carbon sources of energy, as renewable energies, CO2 capture and storage technologies, smart energy networks and energy efficiency and savings. Future scenarios for 2030 elaborated by the International Energy Agency (IEA) shows as a mix energy plan could reduce the global CO2 emissions from 27Gt to 23 Gt (about 15%). A strategic use of the underground in terms of: - development of CCS (Carbon dioxide Capture and Storage) associated to fossil fuel combustion; - increase of CH4 geological storage sites; - use of renewable energies as geothermic for power generation; could open a new energy scenario, according to the climate models published by IPCC. Nowadays CCS market is mainly developed in USA and Canada, but still not much accounted in Europe. In Italy there aren't active CCS projects, even if potential areas have been already identified. Many CH4 storage sites are located in Northern America, while other are present in Europe and Italy, but the number of sites is limited despite the huge underground potentiality. In Italy the power generation from geothermal energy comes exclusively from Tuscany (Larderello-Travale and Mt. Amiata geothermal fields) despite the huge potentiality of other regions as Latium, Campania and Sicily (Central and South Italy). The energy deficit and the relevant CO2 emissions represent a common status for many Italian regions, especially for the Latium Region. This suggests that a new energy plan to improve the efficiency and the environmental sustainability is necessary. The evaluations of potential areas suitable for CO2 and/or CH4 geological storage and geothermal energy in the Latium region, have been done through a revisiting of public data such as well composite logs and maps. For the selection has been taken in account too, exclusion criteria sites as well as presence of geological risks and natural protected areas. Then the storage capacity and geothermal potentiality have been estimated for the selected areas. Finally, considering the hypothesized energy mix plan, an evaluation of the potential CO2 emissions decrease has been done. Preliminary results are encouraging to extent this evaluation also in other regions to improve a National Energy Plan.

Development of Mesoporous Nanocatalysts for Production of Hydrogen and Fisher Tropsch Studies

NASA Astrophysics Data System (ADS)

Abrokwah, Richard Yeboah

The primary aim of this study was to develop mesoporous nanocatalysts for (i) hydrogen production via steam reforming of methanol (SRM) in a tubular reactor, and (ii) syngas conversion to hydrocarbons via Fisher-Tropsch synthesis using silicon microchannel microreactors. The mesoporous catalysts for SRM were prepared by an optimized one-pot hydrothermal synthesis procedure. The catalysts were investigated for SRM activity in a packed bed tubular reactor using metals, namely, Cu, Co, Ni, Pd, Zn, and Sn. The metals were incorporated in different supports -MCM-41, SBA-15, CeO2, TiO2, and ZrO2 to investigate the influence of support on catalyst properties. A sharp contrast in catalyst performance was noticed depending on the type of support employed. For example, in SRM at 250 °C, Cu supported on amorphous silica SBA-15 and MCM-41 produced significantly less CO (< 7%) compared to other crystalline supports Cu-TiO2 and Cu/ZrO2 that showed high CO selectivity of ˜56% and ˜37%, respectively. Amongst all the metals studied for SRM activity using 1:3 methanol:water mole ratio at 250 °C, 10%Cu-MCM-41 showed the best performance with 68% methanol conversion, 100% H2 , ˜6 % CO, 94% CO2 selectivities, and no methane formation. Furthermore, 10%Cu-CeO2 yielded the lowest CO selectivity of 1.84% and the highest CO2 selectivity of ˜98% at 250 °C. Stability studies of the catalysts conducted for time-on-stream of 40 h at 300 °C revealed that Cu-MCM41 was the most stable and displayed consistent steady state conversion of ˜74%. Our results indicate that, although coking played an influential role in deactivation of most catalysts, thermal sintering and changes in MCM-41 structure can be responsible for the catalyst deactivation. For monomtetallic systems, the MCM-41 supported catalysts especially Pd and Sn showed appreciable hydrothermal stability under the synthesis and reaction conditions. While bimetallic Pd-Co-MCM-41 and Cu-Ni-MCM-41 catalysts produced more CO, Cu-Zn-MCM-41 and Cu-Sn-MCM-41exhibited better SRM activity, and produced much less CO and CH4. In spite of the improved the stability and dispersion of the monometallic active sites in the support, no noticeable synergistic activity was observed in terms of H2 and CO selectivities in the multimetallic catalysts. For the Fisher-Tropsch (F-T) studies, Co-TiO 2, Fe-TiO2 and Ru-TiO2 catalysts were prepared by the sol-gel method and coated on 116 microchannels (50mum wide x 100mum deep) of a Si-microreactor. The F-T process parameters such as temperature, pressure and flow rates were controlled by an in-house setup programmed by LabVIEWRTM. The effect of temperature on F-T activity in the range of 150 to 300°C was investigated at 1 atm, a flow rate of 6 ml/min and a constant H2:CO molar ratio of 2:1. In our initial studies at 220 °C, 12%Ru-TiO2 showed higher CO conversion of 74% and produced the highest C2-C4 hydrocarbon selectivity-of ˜11% ethane, 22% propane and ˜17% butane. The overall catalyst stability and performance was in the order of 12%Ru-TiO2>> 12%Fe-TiO2 > 12%Co-TiO2.

Highly Surface-Active Ca(OH)2 Monolayer as a CO2 Capture Material.

PubMed

Özçelik, V Ongun; Gong, Kai; White, Claire E

2018-03-14

Greenhouse gas emissions originating from fossil fuel combustion contribute significantly to global warming, and therefore the design of novel materials that efficiently capture CO 2 can play a crucial role in solving this challenge. Here, we show that reducing the dimensionality of bulk crystalline portlandite results in a stable monolayer material, named portlandene, that is highly effective at capturing CO 2 . On the basis of theoretical analysis comprised of ab initio quantum mechanical calculations and force-field molecular dynamics simulations, we show that this single-layer phase is robust and maintains its stability even at high temperatures. The chemical activity of portlandene is seen to further increase upon defect engineering of its surface using vacancy sites. Defect-containing portlandene is capable of separating CO and CO 2 from a syngas (CO/CO 2 /H 2 ) stream, yet is inert to water vapor. This selective behavior and the associated mechanisms have been elucidated by examining the electronic structure, local charge distribution, and bonding orbitals of portlandene. Additionally, unlike conventional CO 2 capturing technologies, the regeneration process of portlandene does not require high temperature heat treatment because it can release the captured CO 2 by application of a mild external electric field, making portlandene an ideal CO 2 capturing material for both pre- and postcombustion processes.

Viability and adaptation potential of indigenous microorganisms from natural gas field fluids in high pressure incubations with supercritical CO2.

PubMed

Frerichs, Janin; Rakoczy, Jana; Ostertag-Henning, Christian; Krüger, Martin

2014-01-21

Carbon Capture and Storage (CCS) is currently under debate as large-scale solution to globally reduce emissions of the greenhouse gas CO2. Depleted gas or oil reservoirs and saline aquifers are considered as suitable reservoirs providing sufficient storage capacity. We investigated the influence of high CO2 concentrations on the indigenous bacterial population in the saline formation fluids of a natural gas field. Bacterial community changes were closely examined at elevated CO2 concentrations under near in situ pressures and temperatures. Conditions in the high pressure reactor systems simulated reservoir fluids i) close to the CO2 injection point, i.e. saturated with CO2, and ii) at the outer boundaries of the CO2 dissolution gradient. During the incubations with CO2, total cell numbers remained relatively stable, but no microbial sulfate reduction activity was detected. After CO2 release and subsequent transfer of the fluids, an actively sulfate-respiring community was re-established. The predominance of spore-forming Clostridiales provided evidence for the resilience of this taxon against the bactericidal effects of supercritical (sc)CO2. To ensure the long-term safety and injectivity, the viability of fermentative and sulfate-reducing bacteria has to be considered in the selection, design, and operation of CCS sites.

Comparison of Fracture Gradient Methods for the FutureGen 2.0 Carbon Storage Site, Ill., USA.

NASA Astrophysics Data System (ADS)

Appriou, D.; Spane, F.; Wurstner White, S.; Kelley, M. E.; Sullivan, E. C.; Bonneville, A.; Gilmore, T. J.

2014-12-01

As part of a first-of-its-kind carbon dioxide storage project, FutureGen Industrial Alliance is planning to inject 1.1 MMt/yr of supercritical CO2 over a 20-year period within a 1240 m deep saline aquifer (Mount Simon Sandstone) located in Morgan County, Illinois, USA. Numerous aspects of the design and operational activities of the CO2 storage site are dependent on the geomechanical properties of the targeted reservoir zone, as well as of the overlying confining zone and the underlying crystalline Precambrian basement. Detailed determination of the state-of-stress within the subsurface is of paramount importance in successfully designing well drilling/completion aspects, as well as assessing the risk of induced seismicity and the potential for creating and/or reopening pre-existing fractures; all of which help ensure the safe long-term storage of injected CO2. The quantitative determination of the subsurface fracture gradient is one of the key geomechanical parameters for the site injection design and operational limits (e.g., maximum safe injection pressure). A characterization well drilled in 2011 provides subsurface geomechanical characterization information for the FutureGen 2.0 site, and includes: 1) continuous elastic properties inferred from sonic/acoustic wireline logs 2) discrete depth geomechanical laboratory core measurements and 3) results obtained from hydraulic fracturing tests of selected borehole/depth-intervals. In this paper, the precise fracture gradients derived from borehole geomechanical test results are compared with semi-empirical, fracture gradient calculation/relationships based on elastic property wireline surveys and laboratory geomechanical core test results. Implications for using various fracture-gradients obtained from the different methods are assessed using PNNL's subsurface multiphase flow and transport simulator STOMP-CO2. The implications for operational activities at the site (based on using different fracture gradients) are also discussed.

Estimation of CO2 emission from water treatment plant--model development and application.

PubMed

Kyung, Daeseung; Kim, Dongwook; Park, Nosuk; Lee, Woojin

2013-12-15

A comprehensive mathematical model developed for this study was used to compare estimates of on-site and off-site CO2 emissions, from conventional and advanced water treatment plants (WTPs). When 200,000 m(3) of raw water at 10 NTU (Nepthelometric Turbidity Unit) was treated by a conventional WTP to 0.1 NTU using aluminum sulfate as a coagulant, the total CO2 emissions were estimated to be 790 ± 228 (on-site) and 69,596 ± 3950 (off-site) kg CO2e/d. The emissions from an advanced WTP containing micro-filtration (MF) membrane and ozone disinfection processes; treating the same raw water to 0.005 NTU, were estimated to be 395 ± 115 (on-site) and 38,197 ± 2922 (off-site) kg CO2e/d. The on-site CO2 emissions from the advanced WTP were half that from the conventional WTP due to much lower use of coagulant. On the other hand, off-site CO2 emissions due to consumption of electricity were 2.14 times higher for the advanced WTP, due to the demands for operation of the MF membrane and ozone disinfection processes. However, the lower use of chemicals in the advanced WTP decreased off-site CO2 emissions related to chemical production and transportation. Overall, total CO2 emissions from the conventional WTP were 1.82 times higher than that from the advanced WTP. A sensitivity analysis was performed for the advanced WTP to suggest tactics for simultaneously reducing CO2 emissions further and enhancing water quality. Copyright © 2013 Elsevier Ltd. All rights reserved.

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

PubMed Central

2011-01-01

This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

Poisoning of a Silica-Supported Cobalt Catalyst due to Presence of Sulfur Impurities in Syngas during Fischer–Tropsch Synthesis: Effects of Chelating Agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bambal, Ashish S.; Guggilla, Vidya S.; Kugler, Edwin L.

2014-04-09

The effects of sulfur impurities on the performance of cobalt-based Fischer–Tropsch catalysts are evaluated under industrially relevant operating conditions of temperature, pressure, and impurity levels. Chelating agents (CAs) were used to modify the SiO 2 support, and the performances of the CA-modified catalysts are compared with conventional Co/SiO 2 catalysts. For both the Co/SiO 2 and CA-modified catalysts, the presence of sulfur in the inlet syngas results in a notable drop in the CO conversion, an undesired shift in the hydrocarbon selectivity toward short-chain hydrocarbons, more olefins in the products, and lower product yields. In the post-poisoning stage, i.e., aftermore » termination of sulfur introduction in the inlet syngas, the CA-modified catalysts recover activity and selectivity (to some extent at least), whereas such trends are not observed for the base-case, i.e., unmodified Co/SiO 2 catalyst. Finally, the improved performance of the CA-modified catalysts in the presence of sulfur is attributed to higher densities of active sites.« less

Analysis of the potential of near-ground measurements of CO2 and CH4 in London, UK, for the monitoring of city-scale emissions using an atmospheric transport model

NASA Astrophysics Data System (ADS)

Boon, Alex; Broquet, Grégoire; Clifford, Deborah J.; Chevallier, Frédéric; Butterfield, David M.; Pison, Isabelle; Ramonet, Michel; Paris, Jean-Daniel; Ciais, Philippe

2016-06-01

Carbon dioxide (CO2) and methane (CH4) mole fractions were measured at four near-ground sites located in and around London during the summer of 2012 with a view to investigating the potential of assimilating such measurements in an atmospheric inversion system for the monitoring of the CO2 and CH4 emissions in the London area. These data were analysed and compared with simulations using a modelling framework suited to building an inversion system: a 2 km horizontal resolution south of England configuration of the transport model CHIMERE driven by European Centre for Medium-Range Weather Forecasts (ECMWF) meteorological forcing, coupled to a 1 km horizontal resolution emission inventory (the UK National Atmospheric Emission Inventory). First comparisons reveal that local sources, which cannot be represented in the model at a 2 km resolution, have a large impact on measurements. We evaluate methods to filter out the impact of some of the other critical sources of discrepancies between the measurements and the model simulation except that of the errors in the emission inventory, which we attempt to isolate. Such a separation of the impact of errors in the emission inventory should make it easier to identify the corrections that should be applied to the inventory. Analysis is supported by observations from meteorological sites around the city and a 3-week period of atmospheric mixing layer height estimations from lidar measurements. The difficulties of modelling the mixing layer depth and thus CO2 and CH4 concentrations during the night, morning and late afternoon lead to focusing on the afternoon period for all further analyses. The discrepancies between observations and model simulations are high for both CO2 and CH4 (i.e. their root mean square (RMS) is between 8 and 12 parts per million (ppm) for CO2 and between 30 and 55 parts per billion (ppb) for CH4 at a given site). By analysing the gradients between the urban sites and a suburban or rural reference site, we are able to decrease the impact of uncertainties in the fluxes and transport outside the London area and in the model domain boundary conditions. We are thus able to better focus attention on the signature of London urban CO2 and CH4 emissions in the atmospheric CO2 and CH4 concentrations. This considerably improves the statistical agreement between the model and observations for CO2 (with model-data RMS discrepancies that are between 3 and 7 ppm) and to a lesser degree for CH4 (with model-data RMS discrepancies that are between 29 and 38 ppb). Between one of the urban sites and either the rural or suburban reference site, selecting the gradients during periods wherein the reference site is upwind of the urban site further decreases the statistics of the discrepancies in general, though not systematically. In a further attempt to focus on the signature of the city anthropogenic emission in the mole fraction measurements, we use a theoretical ratio of gradients of carbon monoxide (CO) to gradients of CO2 from fossil fuel emissions in the London area to diagnose observation-based fossil fuel CO2 gradients, and compare them with the fossil fuel CO2 gradients simulated with CHIMERE. This estimate increases the consistency between the model and the measurements when considering only one of the two urban sites, even though the two sites are relatively close to each other within the city. While this study evaluates and highlights the merit of different approaches for increasing the consistency between the mesoscale model and the near-ground data, and while it manages to decrease the random component of the analysed model-data discrepancies to an extent that should not be prohibitive to extracting the signal from the London urban emissions, large biases, the sign of which depends on the measurement sites, remain in the final model-data discrepancies. Such biases are likely related to local emissions to which the urban near-ground sites are highly sensitive. This questions our current ability to exploit urban near-ground data for the atmospheric inversion of city emissions based on models at spatial resolution coarser than 2 km. Several measurement and modelling concepts are discussed to overcome this challenge.

Molecular Recognition of Fluorine Impacts Substrate Selectivity in the Fluoroacetyl-CoA Thioesterase FlK

PubMed Central

2015-01-01

The fluoroacetate-producing bacterium Streptomyces cattleya has evolved a fluoroacetyl-CoA thioesterase (FlK) that exhibits a remarkably high level of discrimination for its cognate substrate compared to the cellularly abundant analogue acetyl-CoA, which differs only by the absence of the fluorine substitution. A major determinant of FlK specificity derives from its ability to take advantage of the unique properties of fluorine to enhance the reaction rate, allowing fluorine discrimination under physiological conditions where both substrates are likely to be present at saturating concentrations. Using a combination of pH–rate profiles, pre-steady-state kinetic experiments, and Taft analysis of wild-type and mutant FlKs with a set of substrate analogues, we explore the role of fluorine in controlling the enzyme acylation and deacylation steps. Further analysis of chiral (R)- and (S)-[2H1]fluoroacetyl-CoA substrates demonstrates that a kinetic isotope effect (1.7 ± 0.2) is observed for only the (R)-2H1 isomer, indicating that deacylation requires recognition of the prochiral fluoromethyl group to position the α-carbon for proton abstraction. Taken together, the selectivity for the fluoroacetyl-CoA substrate appears to rely not only on the enhanced polarization provided by the electronegative fluorine substitution but also on molecular recognition of fluorine in both formation and breakdown of the acyl-enzyme intermediate to control active site reactivity. These studies provide insights into the basis of fluorine selectivity in a naturally occurring enzyme–substrate pair, with implications for drug design and the development of fluorine-selective biocatalysts. PMID:24635371

Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bambal, A.S.; Gardner, T.H.; Kugler, E.L.

2012-01-01

Sulfur compounds that are generally found in syngas derived from coal and biomass are a poison to Fischer-Tropsch (FT) catalysts. The presence of sulfur impurities in the ppm range can limit the life of a FT catalyst to a few hours or a few days. In this study, FT synthesis was carried out in a fixed-bed reactor at 230 °C, 20 bar, and 13,500 Ncm3/h/gcat for 72 h using syngas with H2/CO = 2.0. Cobalt-based catalysts were subjected to poisoning by 10 and 50 ppm sulfur in the syngas. The performance of FT catalyst was compared in context of syngasmore » conversion, product selectivities and yields, during the poisoning as well as post-poisoning stages. At both the impurity concentrations, the sulfur was noted to cause permanent loss in the activity, possibly by adsorbing irreversibly on the surface. The sulfur poison affects the hydrogenation and the chain-propagation ability of the catalysts, and shifts the product selectivity towards short-chain hydrocarbons with higher percentages of olefins. Additional diffusion limitations caused due to sulfur poisoning are thought to alter the product selectivity. The shifts in product selectivities suggest that the sulfur decreases the ability of the catalyst to form C-C bonds to produce longer-chain hydrocarbons. The selective blocking of sulfur is thought to affect the hydrogenation ability on the catalyst, resulting in more olefins in the product after sulfur poisoning. The sulfur poisoning on the cobalt catalyst is expected to cause an increase in the number of sites responsible for WGS or to influence the Boudouard reaction, resulting in a higher CO2 selectivity. Both the sites responsible for CO adsorptions as well as the sites for chain growth are poisoned during the poisoning. Additionally, the performance of a base-case cobalt catalyst is compared with that of catalysts modified by chelating agents (CAs). The superior performance of CA-modified catalysts during sulfur poisoning is attributed to the presence of smaller crystallite sizes and higher dispersions of cobalt on the support. Finally, the sulfur deactivation data is modeled by a simple kinetic expression to determine the deactivation constant, deactivation rates and half-life of the FT catalyst.« less

Energy and chemicals from the selective electrooxidation of renewable diols by organometallic fuel cells.

PubMed

Bellini, Marco; Bevilacqua, Manuela; Filippi, Jonathan; Lavacchi, Alessandro; Marchionni, Andrea; Miller, Hamish A; Oberhauser, Werner; Vizza, Francesco; Annen, Samuel P; Grützmacher, H

2014-09-01

Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol (1,2-P), 1,3-propanediol (1,3-P), and 1,4-butanediol (1,4-B) to their corresponding mono-carboxylates. The electrochemical performance of this molecular catalyst is discussed, with the aim to achieve cogeneration of electricity and valuable chemicals in a highly selective electrooxidation from diol precursors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Basin-Scale Hydrologic Impacts of CO2 Storage: Regulatory and Capacity Implications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Birkholzer, J.T.; Zhou, Q.

Industrial-scale injection of CO{sub 2} into saline sedimentary basins will cause large-scale fluid pressurization and migration of native brines, which may affect valuable groundwater resources overlying the deep sequestration reservoirs. In this paper, we discuss how such basin-scale hydrologic impacts can (1) affect regulation of CO{sub 2} storage projects and (2) may reduce current storage capacity estimates. Our assessment arises from a hypothetical future carbon sequestration scenario in the Illinois Basin, which involves twenty individual CO{sub 2} storage projects in a core injection area suitable for long-term storage. Each project is assumed to inject five million tonnes of CO{sub 2}more » per year for 50 years. A regional-scale three-dimensional simulation model was developed for the Illinois Basin that captures both the local-scale CO{sub 2}-brine flow processes and the large-scale groundwater flow patterns in response to CO{sub 2} storage. The far-field pressure buildup predicted for this selected sequestration scenario suggests that (1) the area that needs to be characterized in a permitting process may comprise a very large region within the basin if reservoir pressurization is considered, and (2) permits cannot be granted on a single-site basis alone because the near- and far-field hydrologic response may be affected by interference between individual sites. Our results also support recent studies in that environmental concerns related to near-field and far-field pressure buildup may be a limiting factor on CO{sub 2} storage capacity. In other words, estimates of storage capacity, if solely based on the effective pore volume available for safe trapping of CO{sub 2}, may have to be revised based on assessments of pressure perturbations and their potential impact on caprock integrity and groundwater resources, respectively. We finally discuss some of the challenges in making reliable predictions of large-scale hydrologic impacts related to CO{sub 2} sequestration projects.« less

Discovery of (pyridin-4-yl)-2H-tetrazole as a novel scaffold to identify highly selective matrix metalloproteinase-13 inhibitors for the treatment of osteoarthritis.

PubMed

Schnute, Mark E; O'Brien, Patrick M; Nahra, Joe; Morris, Mark; Howard Roark, W; Hanau, Cathleen E; Ruminski, Peter G; Scholten, Jeffrey A; Fletcher, Theresa R; Hamper, Bruce C; Carroll, Jeffery N; Patt, William C; Shieh, Huey S; Collins, Brandon; Pavlovsky, Alexander G; Palmquist, Katherine E; Aston, Karl W; Hitchcock, Jeffrey; Rogers, Michael D; McDonald, Joseph; Johnson, Adam R; Munie, Grace E; Wittwer, Arthur J; Man, Chiu-Fai; Settle, Steven L; Nemirovskiy, Olga; Vickery, Lillian E; Agawal, Arun; Dyer, Richard D; Sunyer, Teresa

2010-01-15

Potent, highly selective and orally-bioavailable MMP-13 inhibitors have been identified based upon a (pyridin-4-yl)-2H-tetrazole scaffold. Co-crystal structure analysis revealed that the inhibitors bind at the S(1)(') active site pocket and are not ligands for the catalytic zinc atom. Compound 29b demonstrated reduction of cartilage degradation biomarker (TIINE) levels associated with cartilage protection in a preclinical rat osteoarthritis model. Copyright 2009 Elsevier Ltd. All rights reserved.

Heterogeneous Electrocatalyst with Molecular Cobalt Ions Serving as the Center of Active Sites.

PubMed

Wang, Jiong; Ge, Xiaoming; Liu, Zhaolin; Thia, Larissa; Yan, Ya; Xiao, Wei; Wang, Xin

2017-02-08

Molecular Co 2+ ions were grafted onto doped graphene in a coordination environment, resulting in the formation of molecularly well-defined, highly active electrocatalytic sites at a heterogeneous interface for the oxygen evolution reaction (OER). The S dopants of graphene are suggested to be one of the binding sites and to be responsible for improving the intrinsic activity of the Co sites. The turnover frequency of such Co sites is greater than that of many Co-based nanostructures and IrO 2 catalysts. Through a series of carefully designed experiments, the pathway for the evolution of the Co cation-based molecular catalyst for the OER was further demonstrated on such a single Co-ion site for the first time. The Co 2+ ions were successively oxidized to Co 3+ and Co 4+ states prior to the OER. The sequential oxidation was coupled with the transfer of different numbers of protons/hydroxides and generated an active Co 4+ ═O fragment. A side-on hydroperoxo ligand of the Co 4+ site is proposed as a key intermediate for the formation of dioxygen.

A single-ligand ultra-microporous MOF for precombustion CO2 capture and hydrogen purification.

PubMed

Nandi, Shyamapada; De Luna, Phil; Daff, Thomas D; Rother, Jens; Liu, Ming; Buchanan, William; Hawari, Ayman I; Woo, Tom K; Vaidhyanathan, Ramanathan

2015-12-01

Metal organic frameworks (MOFs) built from a single small ligand typically have high stability, are rigid, and have syntheses that are often simple and easily scalable. However, they are normally ultra-microporous and do not have large surface areas amenable to gas separation applications. We report an ultra-microporous (3.5 and 4.8 Å pores) Ni-(4-pyridylcarboxylate)2 with a cubic framework that exhibits exceptionally high CO2/H2 selectivities (285 for 20:80 and 230 for 40:60 mixtures at 10 bar, 40°C) and working capacities (3.95 mmol/g), making it suitable for hydrogen purification under typical precombustion CO2 capture conditions (1- to 10-bar pressure swing). It exhibits facile CO2 adsorption-desorption cycling and has CO2 self-diffusivities of ~3 × 10(-9) m(2)/s, which is two orders higher than that of zeolite 13X and comparable to other top-performing MOFs for this application. Simulations reveal a high density of binding sites that allow for favorable CO2-CO2 interactions and large cooperative binding energies. Ultra-micropores generated by a small ligand ensures hydrolytic, hydrostatic stabilities, shelf life, and stability toward humid gas streams.

Robust extraction of baseline signal of atmospheric trace species using local regression

NASA Astrophysics Data System (ADS)

Ruckstuhl, A. F.; Henne, S.; Reimann, S.; Steinbacher, M.; Vollmer, M. K.; O'Doherty, S.; Buchmann, B.; Hueglin, C.

2012-11-01

The identification of atmospheric trace species measurements that are representative of well-mixed background air masses is required for monitoring atmospheric composition change at background sites. We present a statistical method based on robust local regression that is well suited for the selection of background measurements and the estimation of associated baseline curves. The bootstrap technique is applied to calculate the uncertainty in the resulting baseline curve. The non-parametric nature of the proposed approach makes it a very flexible data filtering method. Application to carbon monoxide (CO) measured from 1996 to 2009 at the high-alpine site Jungfraujoch (Switzerland, 3580 m a.s.l.), and to measurements of 1,1-difluoroethane (HFC-152a) from Jungfraujoch (2000 to 2009) and Mace Head (Ireland, 1995 to 2009) demonstrates the feasibility and usefulness of the proposed approach. The determined average annual change of CO at Jungfraujoch for the 1996 to 2009 period as estimated from filtered annual mean CO concentrations is -2.2 ± 1.1 ppb yr-1. For comparison, the linear trend of unfiltered CO measurements at Jungfraujoch for this time period is -2.9 ± 1.3 ppb yr-1.

Ni2+-binding RNA motifs with an asymmetric purine-rich internal loop and a G-A base pair.

PubMed Central

Hofmann, H P; Limmer, S; Hornung, V; Sprinzl, M

1997-01-01

RNA molecules with high affinity for immobilized Ni2+ were isolated from an RNA pool with 50 randomized positions by in vitro selection-amplification. The selected RNAs preferentially bind Ni2+ and Co2+ over other cations from first series transition metals. Conserved structure motifs, comprising about 15 nt, were identified that are likely to represent the Ni2+ binding sites. Two conserved motifs contain an asymmetric purine-rich internal loop and probably a mismatch G-A base pair. The structure of one of these motifs was studied with proton NMR spectroscopy and formation of the G-A pair at the junction of helix and internal loop was demonstrated. Using Ni2+ as a paramagnetic probe, a divalent metal ion binding site near this G-A base pair was identified. Ni2+ ions bound to this motif exert a specific stabilization effect. We propose that small asymmetric purine-rich loops that contain a G-A interaction may represent a divalent metal ion binding site in RNA. PMID:9409620

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.

PubMed

Baddour, Frederick G; Nash, Connor P; Schaidle, Joshua A; Ruddy, Daniel A

2016-07-25

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9±0.4 nm α-MoC1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC1-x and β-Mo2 C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. The hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural characterization of framework-gas interactions in the metal-organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction.

PubMed

Gonzalez, Miguel I; Mason, Jarad A; Bloch, Eric D; Teat, Simon J; Gagnon, Kevin J; Morrison, Gregory Y; Queen, Wendy L; Long, Jeffrey R

2017-06-01

The crystallographic characterization of framework-guest interactions in metal-organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4 , N 2 , O 2 , Ar, and P 4 adsorption in Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal-organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co-CH 4 and Co-Ar interactions observed in Co 2 (dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal-CH 4 interaction and the first crystallographically characterized metal-Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co 2 (dobdc), with differential enthalpies of adsorption as weak as -17(1) kJ mol -1 (for Ar). Moreover, the structures of Co 2 (dobdc)·3.8N 2 , Co 2 (dobdc)·5.9O 2 , and Co 2 (dobdc)·2.0Ar reveal the location of secondary (N 2 , O 2 , and Ar) and tertiary (O 2 ) binding sites in Co 2 (dobdc), while high-pressure CO 2 , CO, CH 4 , N 2 , and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.

FutureGen 2.0 Monitoring Program: An Overview of the Monitoring Approach and Technologies Selected for Implementation

DOE PAGES

Vermeul, Vince R.; Strickland, Chris E.; Thorne, Paul D.; ...

2014-12-31

The FutureGen 2.0 Project will design and build a first-of-its-kind, near-zero emissions coal-fueled power plant with carbon capture and storage (CCS). To assess storage site performance and meet the regulatory requirements of the Class VI Underground Injection Control (UIC) Program for CO2 Geologic Sequestration, the FutureGen 2.0 project will implement a suite of monitoring technologies designed to 1) evaluate CO2 mass balance and 2) detect any unforeseen loss in CO2 containment. The monitoring program will include direct monitoring of the injection stream and reservoir, and early-leak-detection monitoring directly above the primary confining zone. It will also implement an adaptive monitoringmore » strategy whereby monitoring results are continually evaluated and the monitoring network is modified as required, including the option to drill additional wells in out-years. Wells will be monitored for changes in CO2 concentration and formation pressure, and other geochemical/isotopic signatures that provide indication of CO2 or brine leakage. Indirect geophysical monitoring technologies that were selected for implementation include passive seismic, integrated surface deformation, time-lapse gravity, and pulsed neutron capture logging. Near-surface monitoring approaches that have been initiated include surficial aquifer and surface- water monitoring, soil-gas monitoring, atmospheric monitoring, and hyperspectral data acquisition for assessment of vegetation conditions. Initially, only the collection of baseline data sets is planned; the need for additional near- surface monitoring will be continually evaluated throughout the design and operational phases of the project, and selected approaches may be reinstituted if conditions warrant. Given the current conceptual understanding of the subsurface environment, early and appreciable impacts to near-surface environments are not expected.« less

Probing the Lewis acidity and catalytic activity of the metal-organic framework [Cu3(btc)2] (BTC=benzene-1,3,5-tricarboxylate).

PubMed

Alaerts, Luc; Séguin, Etienne; Poelman, Hilde; Thibault-Starzyk, Frédéric; Jacobs, Pierre A; De Vos, Dirk E

2006-09-25

An optimized procedure was designed for the preparation of the microporous metal-organic framework (MOF) [Cu3(btc)2] (BTC=benzene-1,3,5-tricarboxylate). The crystalline material was characterized by X-ray diffraction, optical microscopy, SEM, X-ray photoelectron spectroscopy, N2 sorption, thermogravimetry, and IR spectroscopy of adsorbed CO. CO adsorbs on a small number of Cu2O impurities, and particularly on the free CuII coordination sites in the framework. [Cu3(btc)2] is a highly selective Lewis acid catalyst for the isomerization of terpene derivatives, such as the rearrangement of alpha-pinene oxide to campholenic aldehyde and the cyclization of citronellal to isopulegol. By using the ethylene ketal of 2-bromopropiophenone as a test substrate, it was demonstrated that the active sites in [Cu3(btc)2] are hard Lewis acids. Catalyst stability, re-usability, and heterogeneity are critically assessed.

Reduced SnO2 Porous Nanowires with a High Density of Grain Boundaries as Catalysts for Efficient Electrochemical CO2 -into-HCOOH Conversion.

PubMed

Kumar, Bijandra; Atla, Veerendra; Brian, J Patrick; Kumari, Sudesh; Nguyen, Tu Quang; Sunkara, Mahendra; Spurgeon, Joshua M

2017-03-20

Electrochemical conversion of CO 2 into energy-dense liquids, such as formic acid, is desirable as a hydrogen carrier and a chemical feedstock. SnO x is one of the few catalysts that reduce CO 2 into formic acid with high selectivity but at high overpotential and low current density. We show that an electrochemically reduced SnO 2 porous nanowire catalyst (Sn-pNWs) with a high density of grain boundaries (GBs) exhibits an energy conversion efficiency of CO 2 -into-HCOOH higher than analogous catalysts. HCOOH formation begins at lower overpotential (350 mV) and reaches a steady Faradaic efficiency of ca. 80 % at only -0.8 V vs. RHE. A comparison with commercial SnO 2 nanoparticles confirms that the improved CO 2 reduction performance of Sn-pNWs is due to the density of GBs within the porous structure, which introduce new catalytically active sites. Produced with a scalable plasma synthesis technology, the catalysts have potential for application in the CO 2 conversion industry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Declining Atmospheric pCO2 During the Late Miocene and Early Pliocene: New Insights from Paired Alkenone and Coccolith Stable Isotope Barometry

NASA Astrophysics Data System (ADS)

Phelps, S. R.; Polissar, P. J.; deMenocal, P. B.; Swann, J. P.; Guo, M. Y.; Stoll, H. M.

2015-12-01

The relationship between atmospheric CO2 concentrations and climate is broadly understood for the Cenozoic era: warmer periods are associated with higher atmospheric carbon dioxide. This understanding is supported by atmospheric samples of the past 800,000 years from ice cores, which suggest CO2 levels play a key role in regulating global climate on glacial interglacial timescales as well. In this context, the late Miocene poses a challenge: sea-surface temperatures indicate substantial global warmth, though existing data suggest atmospheric CO2 concentrations were lower than pre-industrial values. Recent work using the stable carbon and oxygen isotopic composition of coccolith calcite has demonstrated these organisms began actively diverting inorganic carbon away from calcification and to the site of photosynthesis during the late Miocene. This process occurs in culture experiments in response to low aqueous CO2 concentrations, and suggests decreasing atmospheric pCO2 values during the late Miocene. Here we present new data from ODP Site 806 in the western equatorial Pacific Ocean that supports declining atmospheric CO2 across the late Miocene. Carbon isotope values of coccolith calcite from Site 806 demonstrate carbon limitation and re-allocation of inorganic carbon to photosynthesis starting between ~8 and 6 Ma. The timing of this limitation at Site 806 precedes shifts at other ODP sites, reflecting the higher mixed layer temperature and resultant lower CO2 solubility at Site 806. New measurements of carbon isotope values from alkenones at Site 806 show an increase in photosynthetic carbon fractionation (ɛp) accompanied the carbon limitation evident from coccolith calcite stable isotope data. While higher ɛp is typically interpreted as higher CO2 concentrations, at Site 806, our data suggest it reflects enhancement of chloroplast CO2 from active carbon transport by the coccolithophore algae in response to lower CO2 concentrations. Our new data from ODP Site 806 combined with previous published measurements suggests atmospheric CO2 values declined across the late Miocene and early Pliocene. This decline is coincident with decreasing ocean temperatures suggesting the fundamental relationship between atmospheric CO2 and climate can qualitatively explain late Miocene warmth.

Short-term effects of rainfall on CO2 fluxes above rangelands dominated by Artemisia, Bromus tectorum, and Agropyron

NASA Astrophysics Data System (ADS)

Ivans, S.; Saliendra, N. Z.; Johnson, D. A.

2003-04-01

The short-term effects of rainfall on carbon dioxide (CO_2) fluxes have not been well documented in rangelands of the Intermountain Region of the western USA. We used the Bowen ratio-energy balance technique to continuously measure CO_2 fluxes above three rangeland sites in Idaho and Utah dominated by: 1) Artemisia (sagebrush) near Malta, Idaho; 2) Bromus tectorum (cheatgrass) near Malta, Idaho; and 3) Agropyron (crested wheatgrass) in Rush Valley, Utah. We examined CO_2 fluxes immediately before and after rainfall during periods of 10--19 July 2001 (Summer), 8--17 October 2001 (Autumn), and 16--30 May 2002 (Spring). On sunny days before rainfall during Spring, all three sites were sinks for CO_2. After rainfall in Spring, all three sites became sources of CO_2 for about two days and after that became CO_2 sinks again. During Summer and Autumn when water was limiting, sites were small sources of CO_2 and became larger sources for one day after rainfall. In all three seasons, daytime CO_2 fluxes decreased and nighttime CO_2 fluxes increased after rainfall, suggesting that rainfall stimulated belowground respiration at all three sites. Results from this study indicated that CO_2 fluxes above rangeland sites in the Intermountain West changed markedly after rainfall, especially during Spring when fluxes were highest. KEY WORDS: Bowen ratio-energy balance, Intermountain West, rangelands, sagebrush, cheatgrass, crested wheatgrass

Atmospheric Fossil Fuel CO2 Traced by Δ(14)C in Beijing and Xiamen, China: Temporal Variations, Inland/Coastal Differences and Influencing Factors.

PubMed

Niu, Zhenchuan; Zhou, Weijian; Wu, Shugang; Cheng, Peng; Lu, Xuefeng; Xiong, Xiaohu; Du, Hua; Fu, Yunchong; Wang, Gehui

2016-06-07

One year of atmospheric Δ(14)CO2 were observed in 2014 in the inland city of Beijing and coastal city of Xiamen, China, to trace temporal CO2ff variations and to determine the factors influencing them. The average CO2ff concentrations at the sampling sites in Beijing and Xiamen were 39.7 ± 36.1 ppm and 13.6 ± 12.3 ppm, respectively. These contributed 75.2 ± 14.6% and 59.1 ± 26.8% to their respective annual ΔCO2 offsets over background CO2 concentrations. Significantly (p < 0.05) high CO2ff values were observed in winter in Beijing. We did not find any significant differences in CO2ff values between weekdays and weekends. Diurnal CO2ff variations were plainly evident, with high values between midnight and 4:00, and during morning and afternoon rush hours. The sampling site in the inland city of Beijing displayed much higher CO2ff inputs and overall temporal variations than the site in the coastal city of Xiamen. The variations of CO2ff at both sites were controlled by a combination of emission sources, topography, and atmospheric dispersion. In particular, diurnal observations at the urban site in Beijing showed that CO2ff was easily accumulated under the southeast wind conditions.

Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle.

PubMed

Zanichelli, Valeria; Dallacasagrande, Luca; Arduini, Arturo; Secchi, Andrea; Ragazzon, Giulio; Silvi, Serena; Credi, Alberto

2018-05-11

Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle-the 'track' ring-endowed with two distinct recognition sites (a bipyridinium and an ammonium) for a calix[6]arene-the 'shuttle' ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site.

Maximum leaf conductance driven by CO2 effects on stomatal size and density over geologic time.

PubMed

Franks, Peter J; Beerling, David J

2009-06-23

Stomatal pores are microscopic structures on the epidermis of leaves formed by 2 specialized guard cells that control the exchange of water vapor and CO(2) between plants and the atmosphere. Stomatal size (S) and density (D) determine maximum leaf diffusive (stomatal) conductance of CO(2) (g(c(max))) to sites of assimilation. Although large variations in D observed in the fossil record have been correlated with atmospheric CO(2), the crucial significance of similarly large variations in S has been overlooked. Here, we use physical diffusion theory to explain why large changes in S necessarily accompanied the changes in D and atmospheric CO(2) over the last 400 million years. In particular, we show that high densities of small stomata are the only way to attain the highest g(cmax) values required to counter CO(2)"starvation" at low atmospheric CO(2) concentrations. This explains cycles of increasing D and decreasing S evident in the fossil history of stomata under the CO(2) impoverished atmospheres of the Permo-Carboniferous and Cenozoic glaciations. The pattern was reversed under rising atmospheric CO(2) regimes. Selection for small S was crucial for attaining high g(cmax) under falling atmospheric CO(2) and, therefore, may represent a mechanism linking CO(2) and the increasing gas-exchange capacity of land plants over geologic time.

Maximum leaf conductance driven by CO2 effects on stomatal size and density over geologic time

PubMed Central

Franks, Peter J.; Beerling, David J.

2009-01-01

Stomatal pores are microscopic structures on the epidermis of leaves formed by 2 specialized guard cells that control the exchange of water vapor and CO2 between plants and the atmosphere. Stomatal size (S) and density (D) determine maximum leaf diffusive (stomatal) conductance of CO2 (gcmax) to sites of assimilation. Although large variations in D observed in the fossil record have been correlated with atmospheric CO2, the crucial significance of similarly large variations in S has been overlooked. Here, we use physical diffusion theory to explain why large changes in S necessarily accompanied the changes in D and atmospheric CO2 over the last 400 million years. In particular, we show that high densities of small stomata are the only way to attain the highest gcmax values required to counter CO2“starvation” at low atmospheric CO2 concentrations. This explains cycles of increasing D and decreasing S evident in the fossil history of stomata under the CO2 impoverished atmospheres of the Permo-Carboniferous and Cenozoic glaciations. The pattern was reversed under rising atmospheric CO2 regimes. Selection for small S was crucial for attaining high gcmax under falling atmospheric CO2 and, therefore, may represent a mechanism linking CO2 and the increasing gas-exchange capacity of land plants over geologic time. PMID:19506250

Surfactant-Assisted Phase-Selective Synthesis of New Cobalt MOFs and Their Efficient Electrocatalytic Hydrogen Evolution Reaction.

PubMed

Wu, Ya-Pan; Zhou, Wei; Zhao, Jun; Dong, Wen-Wen; Lan, Ya-Qian; Li, Dong-Sheng; Sun, Chenghua; Bu, Xianhui

2017-10-09

Reported herein are two new polymorphic Co-MOFs (CTGU-5 and -6) that can be selectively crystallized into the pure 2D or 3D net using an anionic or neutral surfactant, respectively. Each polymorph contains a H 2 O molecule, but differs dramatically in its bonding to the framework, which in turn affects the crystal structure and electrocatalytic performance for hydrogen evolution reaction (HER). Both experimental and computational studies find that 2D CTGU-5 which has coordinates water and more open access to the cobalt site has higher electrocatalytic activity than CTGU-6 with the lattice water. The integration with co-catalysts, such as acetylene black (AB) leads to a composite material, AB&CTGU-5 (1:4) with very efficient HER catalytic properties among reported MOFs. It exhibits superior HER properties including a very positive onset potential of 18 mV, low Tafel slope of 45 mV dec -1 , higher exchange current density of 8.6×10 -4  A cm -2 , and long-term stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heavy metals characteristics of settled particles of streets dust from Diwaniyah City- Qadisiyah Governorate - Southern Iraq

NASA Astrophysics Data System (ADS)

Al-Dabbas, Moutaz A.; Mahdi, Khalid H.; Al-Khafaji, Raad; Obayes, Kawthar H.

2018-05-01

Road-side dust samples were collected from selected areas of Diwaniyah city-Qadisiyah Governorate - Southern Iraq. The heavy metals (Fe, Co, Ni, Cu, Zn and Pb) in these streets dust samples were studied and used as indicator for pollution by using three of main indices (I-geo, CF, and PLI). Determination of heavy metal in the roadside dust is with XRD and XRF methods. I-geo for Co, Zn, Pb, and Ni in the studied sites shows relative values of class 1, which indicated the slightly polluted, while I-geo for Fe and Cu shows relative values of class 0, which indicated no pollution. The contamination factor for Co, Zn, Pb, and Ni classified as class 2, which indicate moderately contamination, while the contamination factor for Fe and Cu classified as class 1, which indicate low contamination. PLI values in the all of studied sites classified as class 2 (Deterioration on site quality) indicating local pollution, as well as denote perfection with (class 0) of no pollution. The distribution pattern of metals percentages was affected by gases emitted from transportation vehicles as well as the prevailing wind direction.

Selective, tunable O 2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks

DOE PAGES

Xiao, Dianne J.; Gonzalez, Miguel I.; Darago, Lucy E.; ...

2016-05-16

Here, the air-free reaction of CoCl 2 with 1,3,5-tri(1H- 1,2,3-triazol-5-yl)benzene (H 3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co- BTTri (Co 3[(Co 4Cl) 3(BTTri) 8] 2·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O 2 over N 2, with isosteric heats of adsorption (Q st) of -34(1) and -12(1) kJ/ mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination revealsmore » that O 2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O 2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co 3[(Co 4Cl) 3(BDTriP) 8] 2·DMF; H 3BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O 2 affinities (Q st = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O 2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O 2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.« less

Atmospheric CO2 Records from Sites in the Umweltbundesamt (UBA) Air Sampling Network (1972 - 1997)

DOE Data Explorer

Fricke, W. [Umweltbundesamt, Offenbach/Main, Germany; Wallasch, M. [Umweltbundesamt, Offenbach/Main, Germany; Uhse, Karin [Umweltbundesamt, Offenbach/Main, Germany; Schmidt, Martina [University of Heidelberg, Heidelberg, Germany; Levin, Ingeborg [University of Heidelberg, Heidelberg, Germany

1998-01-01

Air samples for the purpose of monitoring atmospheric CO2 were collected from five sites in the UBA air sampling network. Annual atmospheric CO2 concentrations at Brotjacklriegel rose from 331.63 parts per million by volume (ppmv) in 1972 to 353.12 ppmv in 1988. Because of the site's forest location, the monthly atmospheric CO2 record from Brotjacklriegel exhibits very large seasonal amplitude. This amplitude reached almost 40 ppmv in 1985. Minimum mixing ratios are recorded at Brotjacklriegel during July-September; maximum values, during November-March. CO2 concentrations at Deuselbach rose from 340.82 parts per million by volume (ppmv) in 1972 to 363.76 ppmv in 1989. The monthly atmospheric CO2 record from Deuselbach is influenced by local agricultural activities and photosynthetic depletion but does not exhibit the large seasonal amplitude observed at other UBA monitoring sites. Minimum monthly atmospheric CO2 mixing ratios at Deuselbach are typically observed in August but may appear as early as June. Maximum values are seen in the record for November-March. Atmospheric CO2 concentrations at Schauinsland rose from ~328 parts per million by volume (ppmv) in 1972 to ~365 ppmv in 1997. This represents a growth rate of approximately 1.5 ppmv per year. The Schauinsland site is considered the least contaminated of the UBA sites. CO2 concentrations at Waldhof rose from 346.82 parts per million by volume (ppmv) in 1972 to 372.09 ppmv in 1993. The Waldhof site is subject to pollution sources; consequently, the monthly atmospheric CO2 record exhibits a large seasonal amplitude. Atmospheric CO2 concentrations at Westerland rose from ~329 parts per million by volume (ppmv) in 1973 to ~364 ppmv in 1997. The atmospheric CO2 record from Westerland shows a seasonal pattern similar to other UBA sites; minimum values are recorded during July-September; maximum mixing ratios during November-March.

Relating FTS Catalyst Properties to Performance

NASA Technical Reports Server (NTRS)

Ma, Wenping; Ramana Rao Pendyala, Venkat; Gao, Pei; Jermwongratanachai, Thani; Jacobs, Gary; Davis, Burton H.

2016-01-01

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of ?-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Environmental concern-based site screening of carbon dioxide geological storage in China.

PubMed

Cai, Bofeng; Li, Qi; Liu, Guizhen; Liu, Lancui; Jin, Taotao; Shi, Hui

2017-08-08

Environmental impacts and risks related to carbon dioxide (CO 2 ) capture and storage (CCS) projects may have direct effects on the decision-making process during CCS site selection. This paper proposes a novel method of environmental optimization for CCS site selection using China's ecological red line approach. Moreover, this paper established a GIS based spatial analysis model of environmental optimization during CCS site selection by a large database. The comprehensive data coverage of environmental elements and fine 1 km spatial resolution were used in the database. The quartile method was used for value assignment for specific indicators including the prohibited index and restricted index. The screening results show that areas classified as having high environmental suitability (classes III and IV) in China account for 620,800 km 2 and 156,600 km 2 , respectively, and are mainly distributed in Inner Mongolia, Qinghai and Xinjiang. The environmental suitability class IV areas of Bayingol Mongolian Autonomous Prefecture, Hotan Prefecture, Aksu Prefecture, Hulunbuir, Xilingol League and other prefecture-level regions not only cover large land areas, but also form a continuous area in the three provincial-level administrative units. This study may benefit the national macro-strategic deployment and implementation of CCS spatial layout and environmental management in China.

Selective Catalytic Reduction of NO by NH 3 with WO 3-TiO 2 Catalysts: Influence of Catalyst Synthesis Method

DOE PAGES

He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; ...

2016-02-02

A series of supported WO 3/TiO 2 catalysts was prepared by a new synthesis procedure involving co-precipitation of an aqueous TiO(OH) 2 and (NH 4) 10W 12O 41*5H 2O slurry under controlled pH conditions. The morphological properties, molecular structures, surface acidity and surface chemistry of the supported WO 3/TiO 2 catalysts were determined with BET, in situ Raman, in situ IR and temperature-programmed surface reaction (TPSR) spectroscopy, respectively. Isotopic 18O- 16O exchange demonstrated that tungsten oxide was exclusively present as surface WO x species on the TiO 2 support with mono-oxo W=O coordination. In contrast to previous studies employing impregnationmore » synthesis that found only surface one mono-oxo O=WO 4 site on TiO 2, the co-precipitation procedure resulted in the formation of two distinct surface WO x species: mono-oxo O=WO 4 (~1010-1017 cm -1) on low defect density patches of TiO 2 and a second mono-oxo O=WO 4 (~983-986 cm -1) on high defect density patches of TiO 2. The concentration of the second WO x surface species increases as a function of solution pH. Both surface WOx sites, however, exhibited the same NO/NH 3 SCR reactivity. The co-precipitated WO 3-TiO 2 catalysts synthesized in alkaline solutions exhibited enhanced performance for the NO/NH 3 SCR reaction that is ascribed to the greater number of surface defects on the resulting TiO2 support. For the co-precipitated catalyst prepared at pH10, surface NH 4 + species on Br nsted acid sites were found to be more reactive than surface NH 3* species on Lewis acid sites for SCR of NO with NH 3.« less

Structure of the CCR5 Chemokine Receptor-HIV Entry Inhibitor Maraviroc Complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Qiuxiang; Zhu, Ya; Li, Jian

2013-10-21

The CCR5 chemokine receptor acts as a co-receptor for HIV-1 viral entry. Here we report the 2.7 angstrom–resolution crystal structure of human CCR5 bound to the marketed HIV drug maraviroc. The structure reveals a ligand-binding site that is distinct from the proposed major recognition sites for chemokines and the viral glycoprotein gp120, providing insights into the mechanism of allosteric inhibition of chemokine signaling and viral entry. A comparison between CCR5 and CXCR4 crystal structures, along with models of co-receptor–gp120-V3 complexes, suggests that different charge distributions and steric hindrances caused by residue substitutions may be major determinants of HIV-1 co-receptor selectivity.more » These high-resolution insights into CCR5 can enable structure-based drug discovery for the treatment of HIV-1 infection.« less

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

DOE PAGES

Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.; ...

2015-07-30

CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H 2 reduction of Cu 2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Temperature-programmed desorption of CO on OD-Cu revealed the presence of surface sites with strong CO binding that are distinct from the terraces and stepped sites found on polycrystalline Cu foil. After annealing at 350 °C, the surface-area corrected current density for CO reduction is 44-fold lower and the Faradaic efficiency is less than 5%. These changesmore » are accompanied by a reduction in the proportion of strong CO binding sites. Here, we propose that the active sites for CO reduction on OD-Cu surfaces are strong CO binding sites that are supported by grain boundaries. Uncovering these sites is a first step toward understanding the surface chemistry necessary for efficient CO electroreduction.« less

Surface chemistry characterization of hydrodesulfurization and methanol synthesis model nanocatalysts

NASA Astrophysics Data System (ADS)

Komarneni, Mallikharjuna Rao

Surface science investigations of model catalysts have contributed significantly to heterogeneous catalysis over the past several decades. The unique properties of nanomaterials are being exploited in catalysis for the development of highly active and selective catalysts. Surface science investigations of model catalysts such as inorganic fullerene-like (IF) nanoparticles (NP), inorganic nanotubes (INT), and the oxide-supported nanoclusters are included in this dissertation. Thermal desorption spectroscopy and molecular beam scattering were respectively utilized to study the adsorption kinetics and dynamics of gas phase molecules on catalyst surfaces. In addition, ambient pressure kinetics experiments were performed to characterize the catalytic activity of hydrodesulfurization (HDS) nanocatalysts. The nanocatalysts were characterized with a variety of techniques, including Auger electron spectroscopy, x-ray photoelectron spectroscopy, electron microscopy, and x-ray diffraction. The adsorption kinetics studies of thiophene on novel HDS catalysts provided the first evidence for the presence of different adsorption sites on INT-WS2. Additionally, the adsorption sites on IF-MoS2 NP and silica-supported Mo clusters (Mo/silica) were characterized. Furthermore, the C-S bond activation energy of thiophene on Mo/silica was determined. These studies finally led to the fabrication of Ni/Co coated INT-WS2, which showed good catalytic activity towards HDS of thiophene. The studies of methanol synthesis catalysts include the adsorption kinetics and dynamics studies of CO and CO2 on Cu/silica and silica-supported EBL-fabricated Cu/CuOx nanoclusters. The adsorption dynamics of CO on Cu/silica are modeled within the frame work of the capture zone model (CZM), and the active sites of the silica-supported Au/Cu catalysts are successfully mapped. Studies on EBL model catalysts identify the rims of the CuOx nanoclusters as catalytically active sites. This observation has implications for new methanol catalyst design.

The magnitude of interannual variability of ecosystem photosynthetic capacity is controled by stand age and biodiversity

NASA Astrophysics Data System (ADS)

Musavi, Talie; Migliavacca, Mirco; Mahecha, Miguel D.; Reichstein, Markus; Kattge, Jens; Wirth, Christian; Black, T. Andrew; Janssens, Ivan; Knohl, Alexander; Loustau, Denis; Roupsard, Olivier; Varlagin, Andrej; Rambal, Serge; Cescatti, Alessandro; Gianelle, Damiano; Kondo, Hiroaki; Tamrakar, Rijan

2017-04-01

Gross primary productivity, GPP, the total uptake of carbon dioxide (CO2) by ecosystems via photosynthesis, is the largest flux in the global carbon cycle. The photosynthetic capacity at light saturation (GPPsat) is a fundamental ecosystem functional property and its interannual variability (IAV) is propagated to the net ecosystem exchange of CO2. In this contribution we made use of a variety of data streams consisting of ecosystem-atmosphere CO2 fluxes measured at eddy covariance flux sites with more than 4 years of data, the GPPsat derived at the different sites, information about climate (temperature, precipitation, and water availability index - WAI), biodiversity information and species richness, stand age, and plant traits, nutrient availability indexes derived from field campaigns, ancillary databases, and the literature. We also used data about forest structure derived from satellite products. Sites were selected according to the availability of eddy covariance flux measurements for at least 4 years, information about stand age, canopy cover, canopy height, and species abundance. The resulting global database consisted of 50 sites with different vegetation types across different climatic regions. Considering the importance of the understanding of IAV in CO2 fluxes to improve the predictive capacity of the global carbon cycle we analyzed a range of alternative hypotheses and potential drivers of the magnitude of IAV in GPPsat in forest ecosystems. The results show that the IAV in GPPsat within sites is driven by climate (i.e. fluctuations in air temperature and soil water availability), but the magnitude of IAV in GPPsat is related to ecosystem structure, and more in details to stand age and biodiversity (R2=0.55, p<0.0001). We conclude that irrespective of forest type the IAV of GPPsat in older and more diverse forests is dampened, and is higher in younger forests with few dominant species.

Controlled experiments for dense gas diffusion: Experimental design and execution, model comparison

DOE Office of Scientific and Technical Information (OSTI.GOV)

Egami, R.; Bowen, J.; Coulombe, W.

1995-07-01

An experimental baseline CO2 release experiment at the DOE Spill Test Facility on the Nevada Test Site in Southern Nevada is described. This experiment was unique in its use of CO2 as a surrogate gas representative of a variety of specific chemicals. Introductory discussion places the experiment in historical perspective. CO2 was selected as a surrogate gas to provide a data base suitable for evaluation of model scenarios involving a variety of specific dense gases. The experiment design and setup are described, including design rationale and quality assurance methods employed. Resulting experimental data are summarized. Data usefulness is examined throughmore » a preliminary comparison of experimental results with simulations performed using the SLAV and DEGADIS dense gas models.« less

Method and system to reclaim functional sites on a sorbent contaminated by heat stable salts

DOEpatents

Krutka, Holly; Sjostrom, Sharon; Morris, William J.

2016-03-08

The objective of this invention is to develop a method to reclaim functional sites on a CO.sub.2 sorbent that have reacted with an acid gas (other than CO.sub.2) to form heat stable salts (HSS). HSS are a significant concern for dry sorbent based CO.sub.2 capture because over time the buildup of HSS will reduce the overall functionality of the CO.sub.2 sorbent. A chemical treatment can remove the non-CO.sub.2 acid gas and reclaim functional sites that can then be used for further CO.sub.2 adsorption.

A Polyoxovanadate-Resorcin[4]arene-Based Porous Metal-Organic Framework as an Efficient Multifunctional Catalyst for the Cycloaddition of CO2 with Epoxides and the Selective Oxidation of Sulfides.

PubMed

Lu, Bing-Bing; Yang, Jin; Liu, Ying-Ying; Ma, Jian-Fang

2017-10-02

In this work, we report a new polyoxovanadate-resorcin[4]arene-based metal-organic framework (PMOF), [Co 2 L 0.5 V 4 O 12 ]·3DMF·5H 2 O (1), assembled with a newly functionalized wheel-like resorcin[4]arene ligand (L). 1 features an elegant porous motif and represents a rare example of PMOFs composed of both a resorcin[4]arene ligand and polyoxovanadate. Remarkably, 1 shows open V sites in the channel, which makes 1 an efficient heterogeneous Lewis acid catalyst for the cycloaddition of carbon dioxide to epoxides with high conversion and selectivity. Strikingly, 1 also exhibits high catalytic activity for the heterogeneous oxidative desulfurization of sulfides. Particularly, the heterogeneous catalyst 1 can be easily separated and reused with good catalytic activity.

Resource Evaluation and Site Selection for Microalgae Production in India

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milbrandt, A.; Jarvis, E.

2010-09-01

The study evaluates climate conditions, availability of CO2 and other nutrients, water resources, and land characteristics to identify areas in India suitable for algae production. The purpose is to provide an understanding of the resource potential in India for algae biofuels production and to assist policymakers, investors, and industry developers in their future strategic decisions.

Winter CO2 efflux from cold semiarid sagebrush shrublands distributed across the rain-to-snow transition zone

NASA Astrophysics Data System (ADS)

Fellows, A.; Flerchinger, G. N.; Lohse, K. A.; Seyfried, M. S.

2017-12-01

Predicting winter CO2 efflux across the rain-to-snow transition zone is challenging in the cold semiarid northern Great Basin, USA, complicated by steep environmental gradients and marked heterogeneity in ecosystem properties. We therefore examined winter CO2 efflux over 9 site-years using 4 eddy covariance towers located in the Reynolds Creek Critical Zone Observatory. The sites were sagebrush shrublands located at 1425, 1680, 2098, and 2111 m, and spanned a large part of the rain-to-snow transition zone. We focused on two objectives. First, we quantified winter CO2 efflux at the sites, and considered how these varied with elevation. Second, we used a within-site and cross-site analysis to examine the biological and physical factors that impact winter CO2 efflux. Winter conditions were identified using temperature, snow depth, and CO2 exchange measurements and included 12,922 observations. The duration of winter conditions increased from 90 to 180 days with elevation. Peak snow depth increased from < 30 to > 100 cm with elevation. Cumulative winter CO2 efflux accounted for > 10% of the total annual CO2 efflux, increased with elevation, and was a key component of net ecosystem production at some sites in some years. The importance of winter CO2 efflux was accentuated by the region's long winters and also dry summers that decreased water availability and decomposition during non-winter periods. Preliminary regressions examining air temperature, soil temperature, wind speed, snow depth, and gross carbon uptake indicated some of these factors control the rate of winter CO2 efflux and require consideration, but that additional work is needed to disentangle co-linearity and assess the importance of these factors within and between sites. These findings suggest a consideration of winter CO2 efflux is warranted in cold winter-wet semiarid ecosystems, particularly where winters are long and non-winter CO2 efflux is strongly limited by water availability.

Engineering Transition-Metal-Coated Tungsten Carbides for Efficient and Selective Electrochemical Reduction of CO2 to Methane.

PubMed

Wannakao, Sippakorn; Artrith, Nongnuch; Limtrakul, Jumras; Kolpak, Alexie M

2015-08-24

The design of catalysts for CO2 reduction is challenging because of the fundamental relationships between the binding energies of the reaction intermediates. Metal carbides have shown promise for transcending these relationships and enabling low-cost alternatives. Herein, we show that directional bonding arising from the mixed covalent/metallic character plays a critical role in governing the surface chemistry. This behavior can be described by consideration of individual d-band components. We use this model to predict efficient catalysts based on tungsten carbide with a sub-monolayer of iron adatoms. Our approach can be used to predict site-preference and binding-energy trends for complex catalyst surfaces. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the Preferred Active Sites of Promoted MoS 2 for Hydrodesulfurization with Minimal Organonitrogen Inhibition

DOE PAGES

Rangarajan, Srinivas; Mavrikakis, Manos

2016-12-14

Hydrodesulfurization is a process to produce ultralow-sulfur diesel fuel. Although promoted molybdenum sulfide (MoS 2) catalysts have been used industrially for several decades, the active site requirements for selective hydrodesulfurization of organosulfur compounds with minimal inhibition by organonitrogen constituents of a real gasoil feed has not been resolved. By using molecular binding energy descriptors derived from plane wave density functional theory calculations for comparative adsorption of organosulfur and organonitrogen compounds, we analyzed more than 20 potential sites on unpromoted and Ni- and Co-promoted MoS 2. We also found that hydrogen sulfide and ammonia are simple descriptors of adsorption of stericallymore » unhindered organosulfur and organonitrogen compounds such as dibenzothiophene and acridine, respectively. Further, organonitrogen compounds in gasoil bind more strongly than organosulfur compounds on all sites except on sites with exposed metal atoms on the corner and sulfur edges of promoted MoS 2. Consequently, these sites are proposed as required for maximum-hydrodesulfurization minimum-inhibition catalysis.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC

A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molarmore » syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic polymethylbenzenes. However, as syngas conversion increases with increasing temperature, selectivity to liquid product diminished. This is attributed, in large part, to increased saturation of the olefinic intermediates over PdZn metal sites. Under all the conditions and catalysts evaluated in this study, generating liquid product in high yield was challenging (<10 wt. % C5+ yield).« less

Geochemical Monitoring Considerations for the FutureGen 2.0 Project

DOE PAGES

Amonette, James E.; Johnson, Timothy A.; Spencer, Clayton F.; ...

2014-12-31

Geochemical monitoring is an essential component of a suite of monitoring technologies designed to evaluate CO2 mass balance and detect possible loss of containment at the FutureGen 2.0 geologic sequestration site near Jacksonville, IL. This presentation gives an overview of the potential geochemical approaches and tracer technologies that were considered, and describes the evaluation process by which the most cost-effective and robust of these were selected for implementation

Discussion of the influence of CO and CH4 in CO2 transport, injection, and storage for CCS technology.

PubMed

Blanco, Sofía T; Rivas, Clara; Bravo, Ramón; Fernández, Javier; Artal, Manuela; Velasco, Inmaculada

2014-09-16

This paper discusses the influence of the noncondensable impurities CO and CH4 on Carbon Capture and Storage (CCS) technology. We calculated and drew conclusions about the impact of both impurities in the CO2 on selected transport, injection, and storage parameters (pipeline pressure drop, storage capacity, etc.), whose analysis is necessary for the safe construction and operation of CO2 pipelines and for the secure long-term geological storage of anthropogenic CO2. To calculate these parameters, it is necessary to acquire data on the volumetric properties and the vapor-liquid equilibrium of the fluid being subjected to CCS. In addition to literature data, we used new experimental data, which are presented here and were obtained for five mixtures of CO2+CO with compositions characteristic of the typical emissions of the E.U. and the U.S.A. Temperatures and pressures are based on relevant CO2 pipeline and geological storage site values. From our experimental results, Peng-Robinson, PC-SAFT, and GERG Equations of State for were validated CO2+CO under the conditions of CCS. We conclude that the concentration of both impurities strongly affects the studied parameters, with CO being the most influential and problematic. The overall result of these negative effects is an increase in the difficulties, risks, and overall costs of CCS.

Orchestrating Bulk Data Movement in Grid Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vazhkudai, SS

2005-01-25

Data Grids provide a convenient environment for researchers to manage and access massively distributed bulk data by addressing several system and transfer challenges inherent to these environments. This work addresses issues involved in the efficient selection and access of replicated data in Grid environments in the context of the Globus Toolkit{trademark}, building middleware that (1) selects datasets in highly replicated environments, enabling efficient scheduling of data transfer requests; (2) predicts transfer times of bulk wide-area data transfers using extensive statistical analysis; and (3) co-allocates bulk data transfer requests, enabling parallel downloads from mirrored sites. These efforts have demonstrated a decentralizedmore » data scheduling architecture, a set of forecasting tools that predict bandwidth availability within 15% error and co-allocation architecture, and heuristics that expedites data downloads by up to 2 times.« less

Predicting mixed-gas adsorption equilibria on activated carbon for precombustion CO2 capture.

PubMed

García, S; Pis, J J; Rubiera, F; Pevida, C

2013-05-21

We present experimentally measured adsorption isotherms of CO2, H2, and N2 on a phenol-formaldehyde resin-based activated carbon, which had been previously synthesized for the separation of CO2 in a precombustion capture process. The single component adsorption isotherms were measured in a magnetic suspension balance at three different temperatures (298, 318, and 338 K) and over a large range of pressures (from 0 to 3000-4000 kPa). These values cover the temperature and pressure conditions likely to be found in a precombustion capture scenario, where CO2 needs to be separated from a CO2/H2/N2 gas stream at high pressure (~1000-1500 kPa) and with a high CO2 concentration (~20-40 vol %). Data on the pure component isotherms were correlated using the Langmuir, Sips, and dual-site Langmuir (DSL) models, i.e., a two-, three-, and four-parameter model, respectively. By using the pure component isotherm fitting parameters, adsorption equilibrium was then predicted for multicomponent gas mixtures by the extended models. The DSL model was formulated considering the energetic site-matching concept, recently addressed in the literature. Experimental gas-mixture adsorption equilibrium data were calculated from breakthrough experiments conducted in a lab-scale fixed-bed reactor and compared with the predictions from the models. Breakthrough experiments were carried out at a temperature of 318 K and five different pressures (300, 500, 1000, 1500, and 2000 kPa) where two different CO2/H2/N2 gas mixtures were used as the feed gas in the adsorption step. The DSL model was found to be the one that most accurately predicted the CO2 adsorption equilibrium in the multicomponent mixture. The results presented in this work highlight the importance of performing experimental measurements of mixture adsorption equilibria, as they are of utmost importance to discriminate between models and to correctly select the one that most closely reflects the actual process.

Analogs of palmitoyl-CoA that are substrates for myristoyl-CoA:protein N-myristoyltransferase.

PubMed

Rudnick, D A; Lu, T; Jackson-Machelski, E; Hernandez, J C; Li, Q; Gokel, G W; Gordon, J I

1992-11-01

Saccharomyces cerevisiae myristoyl-CoA:protein N-myristoyltransferase (Nmt1p; EC 2.3.1.97) is an essential enzyme that is highly selective for myristoyl-CoA in vivo. It is unclear why myristate (C14:0), a rare cellular fatty acid, has been selected for this covalent protein modification over more abundant fatty acids such as palmitate (C16:0), nor is it obvious how the enzyme's acyl-CoA binding site is able to discriminate between these two fatty acids. Introduction of a cis double bond between C5 and C6 of palmitate [(Z)-5-hexadecenoic acid] or a triple bond between C4 and C5 or C6 and C7 (Y4- and Y6-hexadecenoic acids) yields compounds that, when converted to their CoA derivatives, approach the activity of myristoyl-CoA as Nmt1p substrates in vitro. Kinetic studies of 42 C12-C18 fatty acids containing triple bonds, para-phenylene, or a 2,5-furyl group, as well as cis and trans double bonds, suggest that the geometry of the enzyme's acyl-CoA binding site requires that the acyl chain of active substrates assume a bent conformation in the vicinity of C5. Moreover, the distance between C1 and the bend appears to be a critical determinant for optimal positioning of the acyl-CoA in this binding site so that peptide substrates can subsequently bind in the sequential ordered bi-bi reaction mechanism. Identification of active, conformationally restricted analogs of palmitate offers an opportunity to "convert" wild-type or mutant Nmts to palmitoyltransferases so that they can deliver these C16 fatty acids to critical N-myristoylproteins in vivo. nmt181p contains a Gly-451-->Asp mutation, which causes a marked reduction in the enzyme's affinity for myristoyl-CoA. Strains of S. cerevisiae containing nmt1-181 exhibit temperature-sensitive myristic acid auxotrophy: their complete growth arrest at 37 degrees C is relieved when the medium is supplemented with 500 microM C14:0 but not with C16:0. The CoA derivatives of (Z)-5-hexadecenoic and Y6-hexadecynoic acids are as active substrates for the mutant enzyme as myristoyl-CoA at 24 degrees C. However, unlike C16:0, they produce growth arrest of nmt181p-producing cells at this "permissive" temperature, suggesting that these C16 fatty acids do not allow expression of the biological functions of essential S. cerevisiae N-myristoylproteins.

Analogs of palmitoyl-CoA that are substrates for myristoyl-CoA:protein N-myristoyltransferase.

PubMed Central

Rudnick, D A; Lu, T; Jackson-Machelski, E; Hernandez, J C; Li, Q; Gokel, G W; Gordon, J I

1992-01-01

Saccharomyces cerevisiae myristoyl-CoA:protein N-myristoyltransferase (Nmt1p; EC 2.3.1.97) is an essential enzyme that is highly selective for myristoyl-CoA in vivo. It is unclear why myristate (C14:0), a rare cellular fatty acid, has been selected for this covalent protein modification over more abundant fatty acids such as palmitate (C16:0), nor is it obvious how the enzyme's acyl-CoA binding site is able to discriminate between these two fatty acids. Introduction of a cis double bond between C5 and C6 of palmitate [(Z)-5-hexadecenoic acid] or a triple bond between C4 and C5 or C6 and C7 (Y4- and Y6-hexadecenoic acids) yields compounds that, when converted to their CoA derivatives, approach the activity of myristoyl-CoA as Nmt1p substrates in vitro. Kinetic studies of 42 C12-C18 fatty acids containing triple bonds, para-phenylene, or a 2,5-furyl group, as well as cis and trans double bonds, suggest that the geometry of the enzyme's acyl-CoA binding site requires that the acyl chain of active substrates assume a bent conformation in the vicinity of C5. Moreover, the distance between C1 and the bend appears to be a critical determinant for optimal positioning of the acyl-CoA in this binding site so that peptide substrates can subsequently bind in the sequential ordered bi-bi reaction mechanism. Identification of active, conformationally restricted analogs of palmitate offers an opportunity to "convert" wild-type or mutant Nmts to palmitoyltransferases so that they can deliver these C16 fatty acids to critical N-myristoylproteins in vivo. nmt181p contains a Gly-451-->Asp mutation, which causes a marked reduction in the enzyme's affinity for myristoyl-CoA. Strains of S. cerevisiae containing nmt1-181 exhibit temperature-sensitive myristic acid auxotrophy: their complete growth arrest at 37 degrees C is relieved when the medium is supplemented with 500 microM C14:0 but not with C16:0. The CoA derivatives of (Z)-5-hexadecenoic and Y6-hexadecynoic acids are as active substrates for the mutant enzyme as myristoyl-CoA at 24 degrees C. However, unlike C16:0, they produce growth arrest of nmt181p-producing cells at this "permissive" temperature, suggesting that these C16 fatty acids do not allow expression of the biological functions of essential S. cerevisiae N-myristoylproteins. Images PMID:1438240

Contributions of Atmospheric CO and Hydrogen Uptake to Microbial Dynamics on Recent Hawaiian Volcanic Deposits†

PubMed Central

King, Gary M.

2003-01-01

A series of sites were established on Hawaiian volcanic deposits ranging from about 18 to 300 years old. Three sites occurred in areas that supported tropical rain forests; the remaining sites were in areas that supported little or no plant growth. Sites >26 years old consumed atmospheric CO and hydrogen at rates ranging from about 0.2 to 5 mg of CO m−2 day−1 and 0.1 to 4 mg of H2 m−2 day−1, respectively. Respiration, measured as CO2 production, for a subset of the sites ranged from about 40 to >1,400 mg of CO2 m−2 day−1. CO and H2 accounted for about 13 to 25% of reducing equivalent flow for all but a forested site, where neither substrate appeared significant. Based on responses to chloroform fumigation, hydrogen utilization appeared largely due to microbial uptake. In contrast to results for CO and hydrogen, methane uptake occurred consistently only at the forest site. Increasing deposit age was generally accompanied by increasing concentrations of organic matter and microbial biomass, measured as phospholipid phosphate. Exoenzymatic activities (acid and alkaline phosphatases and α- and β-glucosidases) were positively correlated with deposit age in spite of considerable variability within sites. The diversity of substrates utilized in Biolog Ecoplate assays also increased with deposit age, possibly reflecting changes in microbial community complexity. PMID:12839783

Density functional theory study of homologous organometallic molecules of the [RhXL2]2 (X=Cl, Br, or I; L=CO, PH3, or PF3) type

NASA Astrophysics Data System (ADS)

Seuret, P.; Weber, J.; Wesolowski, T. A.

Density functional theory generalized gradient approximation calculations, which were tested in our previous detailed study of [RhCl(PF3)2]2 (Seuret et al., 2003, Phys. Chem. chem. Phys., 5, 268-274), were applied for a series of homologous organometallic compounds of the [RhXL2]2 (X = Cl, Br, or I; L = CO, PH3, or PF3) type. Various properties of the studied compounds were obtained. Optimized geometries of [RhCl(PH3)2]2 and [RhCl(CO)2]2 are in very good agreement with available experimental data. Geometries of other compounds as well as other properties (thermochemistry of selected fragmentation channels, barriers to structural changes, frontier orbitals) which are not available experimentally were predicted. All the considered compounds are not planar. Enforcing planarity of the central [RhX]2 moiety requires only a small energetic cost ranging from 2.2 to 3.9 kcal mol-1. The analysis of frontier orbitals indicates that the metals provide the most favourable site for the electrophilic attack in all considered compounds. The analysis of the shape of the lowest unoccupied molecular orbitals indicates that the halogens and ligands provide the most favourable site for the nucleophilic attack for [RhCl(CO)2]2 or [RhCl(PF3)2]. For [RhBr(PF3)2]2, [RhI(PF3)2]2 and [RhCl(PH3)2]2, the nucleophilic attack on the halogen is less probable. Except for [RhCl(CO)2]2, the least energetically expensive decomposition channel involves initial separation of ligands. For [RhCl(CO)2]2, its decomposition into the RhCl(CO)2 fragments was found to be the least energetically expensive fragmentation reaction which is probably one of the reasons for the known catalytic activity of this compound.

Selective, ultrathin membrane skins prepared by deposition of novel polymer films on porous alumina supports

NASA Astrophysics Data System (ADS)

Balachandra, Anagi Manjula

Membrane-based separations are attractive in industrial processes because of their low energy costs and simple operation. However, low permeabilities often make membrane processes uneconomical. Since flux is inversely proportional to membrane thickness, composite membranes consisting of ultrathin, selective skins on highly permeable supports are required to simultaneously achieve high throughput and high selectivity. However, the synthesis of defect-free skins with thicknesses less than 50 nm is difficult, and thus flux is often limited. Layer-by-layer deposition of oppositely charged polyelectrolytes on porous supports is an attractive method to synthesize ultrathin ion-separation membranes with high flux and high selectivity. The ion-transport selectivity of multilayer polyelectrolyte membranes (MPMs) is primarily due to Donnan exclusion; therefore increase in fixed charge density should yield high selectivity. However, control over charge density in MPMs is difficult because charges on polycations are electrostatically compensated by charges on polyanions, and the net charge in the bulk of these films is small. To overcome this problem, we introduced a templating method to create ion-exchange sites in the bulk of the membrane. This strategy involves alternating deposition of a Cu2+-poly(acrylic acid) complex and poly(allylamine hydrochloride) on a porous alumina support followed by removal of Cu2+ and deprotonation to yield free -COO- ion-exchange sites. Diffusion dialysis studies showed that the Cl-/SO42-. Selectivity of Cu2+-templated membranes is 4-fold higher than that of membranes prepared in the absence of Cu2+. Post-deposition cross-linking of these membranes by heat-induced amide bond formation further increased Cl-/SO42- selectivity to values as high as 600. Room-temperature, surface-initiated atom transfer radical polymerization (ATRP) provides another convenient method for formation of ultrathin polymer skins. This process involves attachment of polymerization initiators to a porous alumina support and subsequent polymerization from these initiators. Because ATRP is a controlled polymerization technique, it yields well-defined polymer films with low polydispersity indices (narrow molecular weight distributions). Additionally, this method is attractive because film thickness can be easily controlled by adjusting polymerization time. Gas-permeability data showed that grafted poly(ethylene glycol dimethacrylate) membranes have a CO 2/CH4 selectivity of 20, whereas poly(2-hydroxyethyl methacrylate) (PHEMA) films grown from a surface have negligible selectivity. However, derivatization of PHEMA with pentadecafluorooctanoyl chloride increases the solubility of CO2 in the membrane and results in a CO2/CH4 selectivity of 9. Although composite PHEMA membranes have no significant gas-transport selectivity, diffusion dialysis studies with PHEMA membranes showed moderate ion-transport selectivities. Cross-linking of PHEMA membranes by reaction with succinyl chloride greatly enhanced anion-transport selectivities while maintaining reasonable flux. The selectivities of these systems demonstrate that alternating polyelectrolyte deposition and surface-initiated ATRP are indeed capable of forming ultrathin, defect-free membrane skins that can potentially be modified for specific separations.

Gas content and composition of gas hydrate from sediments of the southeastern North American continental margin

USGS Publications Warehouse

Lorenson, T.D.; Collett, T.S.

2000-01-01

Gas hydrate samples were recovered from four sites (Sites 994, 995, 996, and 997) along the crest of the Blake Ridge during Ocean Drilling Program (ODP) Leg 164. At Site 996, an area of active gas venting, pockmarks, and chemosynthetic communities, vein-like gas hydrate was recovered from less than 1 meter below seafloor (mbsf) and intermittently through the maximum cored depth of 63 mbsf. In contrast, massive gas hydrate, probably fault filling and/or stratigraphically controlled, was recovered from depths of 260 mbsf at Site 994, and from 331 mbsf at Site 997. Downhole-logging data, along with geochemical and core temperature profiles, indicate that gas hydrate at Sites 994, 995, and 997 occurs from about 180 to 450 mbsf and is dispersed in sediment as 5- to 30-m-thick zones of up to about 15% bulk volume gas hydrate. Selected gas hydrate samples were placed in a sealed chamber and allowed to dissociate. Evolved gas to water volumetric ratios measured on seven samples from Site 996 ranged from 20 to 143 mL gas/mL water to 154 mL gas/mL water in one sample from Site 994, and to 139 mL gas/mL water in one sample from Site 997, which can be compared to the theoretical maximum gas to water ratio of 216. These ratios are minimum gas/water ratios for gas hydrate because of partial dissociation during core recovery and potential contamination with pore waters. Nonetheless, the maximum measured volumetric ratio indicates that at least 71% of the cages in this gas hydrate were filled with gas molecules. When corrections for pore-water contamination are made, these volumetric ratios range from 29 to 204, suggesting that cages in some natural gas hydrate are nearly filled. Methane comprises the bulk of the evolved gas from all sites (98.4%-99.9% methane and 0%-1.5% CO2). Site 996 hydrate contained little CO2 (0%-0.56%). Ethane concentrations differed significantly from Site 996, where they ranged from 720 to 1010 parts per million by volume (ppmv), to Sites 994 and 997, which contained much less ethane (up to 86 ppmv). Up to 19 ppmv propane and other higher homologues were noted; however, these gases are likely contaminants derived from sediment in some hydrate samples. CO2 concentrations are less in gas hydrate than in the surrounding sediment, likely an artifact of core depressurization, which released CO2 derived from dissolved organic carbon (DIC) into sediment. The isotopic composition of methane from gas hydrate ranges from ??13C of -62.5??? to -70.7??? and ??D of -175??? to -200??? and is identical to the isotopic composition of methane from surrounding sediment. Methane of this isotopic composition is mainly microbial in origin and likely produced by bacterial reduction of bicarbonate. The hydrocarbon gases here are likely the products of early microbial diagenesis. The isotopic composition of CO2 from gas hydrate ranges from ??13C of -5.7 to -6.9, about 15??? lighter than CO2 derived from nearby sediment.

Exceptionally High Efficient Co-Co2P@N, P-Codoped Carbon Hybrid Catalyst for Visible Light-Driven CO2-to-CO Conversion.

PubMed

Fu, Wen Gan

2018-05-02

Artificial photosynthesis has attracted wide attention, particularly the development of efficient solar light-driven methods to reduce CO2 to form energy-rich carbon-based products. Because CO2 reduction is an uphill process with a large energy barrier, suitable catalysts are necessary to achieve this transformation. In addition, CO2 adsorption on a catalyst and proton transfer to CO2 are two important factors for the conversion reaction，and catalysts with high surface area and more active sites are required to improve the efficiency of CO2 reduction. Here, we report a visible light-driven system for CO2-to-CO conversion that consists of a heterogeneous hybrid catalyst of Co and Co2P nanoparticles embedded in carbon nanolayers codoped with N and P (Co-Co2P@NPC) and a homogeneous Ru(II)-based complex photosensitizer. The average generation rate of CO of the system was up to 35,000 μmol h-1 g-1 with selectivity of 79.1% in 3 h. Linear CO production at an exceptionally high rate of 63,000 μmol h-1 g-1 was observed in the first hour of reaction. Inspired by this highly active catalyst, we also synthesized Co@NC and Co2P@NPC materials and explored their structure, morphology, and catalytic properties for CO2 photoreduction. The results showed that the nanoparticle size, partially adsorbed H2O molecules on the catalyst surface, and the hybrid nature of the systems influenced their photocatalytic CO2 reduction performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local Structure and Surface Properties of CoxZn1-xO Thin Films for Ozone Gas Sensing.

PubMed

Catto, Ariadne C; Silva, Luís F da; Bernardi, Maria Inês B; Bernardini, Sandrine; Aguir, Khalifa; Longo, Elson; Mastelaro, Valmor R

2016-10-05

A detailed study of the structural, surface, and gas-sensing properties of nanostructured Co x Zn 1-x O films is presented. X-ray diffraction (XRD) analysis revealed a decrease in the crystallization degree with increasing Co content. The X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopies (XPS) revealed that the Co 2+ ions preferentially occupied the Zn 2+ sites and that the oxygen vacancy concentration increased as the amount of cobalt increased. Electrical measurements showed that the Co dopants not only enhanced the sensor response at low ozone levels (ca. 42 ppb) but also led to a decrease in the operating temperature and improved selectivity. The enhancement in the gas-sensing properties was attributed to the presence of oxygen vacancies, which facilitated ozone adsorption.

Identification of a Novel Allosteric Inhibitory Site on Tryptophan Hydroxylase 1 Enabling Unprecedented Selectivity Over all Related Hydroxylases

PubMed Central

Petrassi, Mike; Barber, Rob; Be, Celine; Beach, Sarah; Cox, Brian; D’Souza, Anne-Marie; Duggan, Nick; Hussey, Martin; Fox, Roy; Hunt, Peter; Jarai, Gabor; Kosaka, Takatoshi; Oakley, Paul; Patel, Viral; Press, Neil; Rowlands, David; Scheufler, Clemens; Schmidt, Oliver; Srinivas, Honnappa; Turner, Mary; Turner, Rob; Westwick, John; Wolfreys, Alison; Pathan, Nuzhat; Watson, Simon; Thomas, Matthew

2017-01-01

Pulmonary arterial hypertension (PAH) has demonstrated multi-serotonin receptor dependent pathologies, characterized by increased tone (5-HT1B receptor) and complex lesions (SERT, 5-HT1B, 5-HT2B receptors) of the pulmonary vasculature together with right ventricular hypertrophy, ischemia and fibrosis (5-HT2B receptor). Selective inhibitors of individual signaling elements – SERT, 5-HT2A, 5HT2B, and combined 5-HT2A/B receptors, have all been tested clinically and failed. Thus, inhibition of tryptophan hydroxylase 1 (TPH1), the rate limiting step in 5-HT synthesis, has been suggested as a more broad, and thereby more effective, mode of 5-HT inhibition. However, selectivity over non-pathogenic enzyme family members, TPH2, phenylalanine hydroxylase, and tyrosine hydroxylase has hampered therapeutic development. Here we describe the site/sequence, biochemical, and biophysical characterization of a novel allosteric site on TPH1 through which selectivity over TPH2 and related aromatic amino acid hydroxylases is achieved. We demonstrate the mechanism of action by which novel compounds selectively inhibit TPH1 using surface plasma resonance and enzyme competition assays with both tryptophan ligand and BH4 co-factor. We demonstrate 15-fold greater potency within a human carcinoid cell line versus the most potent known TPH1/2 non-specific inhibitor. Lastly, we detail a novel canine in vivo system utilized to determine effective biologic inhibition of newly synthesized 5-HT. These findings are the first to demonstrate TPH1-selective inhibition and may pave the way to a truly effective means to reduce pathologic 5-HT and thereby treat complex remodeling diseases such as PAH. PMID:28529483

Air pollution over the North China Plain and its implication of regional transport: A new sight from the observed evidences.

PubMed

Ge, Baozhu; Wang, Zifa; Lin, Weili; Xu, Xiaobin; Li, Jie; Ji, Dongshen; Ma, Zhiqiang

2018-03-01

High concentrations of the fine particles (PM 2.5 ) are frequently observed during all seasons over the North China Plain (NCP) region in recent years. In NCP, the contributions of regional transports to certain area, e.g. Beijing city, are often discussed and estimated by models when considering an effective air pollution controlling strategy. In this study, we selected three sites from southwest to northeast in NCP, in which the concentrations of air pollutants displayed a multi-step decreasing trend in space. An approach based on the measurement results at these sites has been developed to calculate the relative contributions of the minimal local emission (MinLEC) and the maximum regional transport (MaxRTC) to the air pollutants (e.g., SO 2 , NO 2 , CO, PM 2.5 ) in Beijing. The minimal influence of local emission is estimated by the difference of the air pollutants' concentrations between urban and rural areas under the assumption of a similar influence of regional transport. Therefore, it's convenient to estimate the contributions of local emission from regional transport based on the selective measurement results instead of the complex numerical model simulation. For the whole year of 2013, the averaged contributions of MinLEC (MaxRTC) for NO 2 , SO 2 , PM 2.5 and CO are 61.7% (30.7%), 46.6% (48%), 52.1% (40.2%) and 35.8% (45.5%), respectively. The diurnal variation of MaxRTC for SO 2 , PM 2.5 and CO shows an increased pattern during the afternoon and reached a peak (more than 50%) around 18:00, which indicates that the regional transport is the important role for the daytime air pollution in Beijing. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effects of ecological restoration on CO2 fluxes from a climatically marginal upland blanket bog

NASA Astrophysics Data System (ADS)

Dixon, Simon; Qassim, Suzane; Rowson, James; Worrall, Fred; Evans, Martin

2013-04-01

A legacy of gully incision, deposition of industrially-derived aerial pollutants, inappropriate management and wildfire has left large expanses of the topographic Bleaklow Plateau (Peak District National Park, England, UK) bare of vegetation and susceptible to massive erosion of the peat soils. The consequence of such degradation has been to decrease the capacity of the peatland on the plateau to provide important ecosystem services including; loss of net C sink function, discolouration of surface waters, mobilisation to surface waters of stored heavy metals and infilling of upland reservoirs with peat-derived sediment. In response to on-going and worsening degradation a programme of ecological restoration has been undertaken. Restoration methods include: seeding with a lawn grass mix; liming; fertilisation; slope stabilisation; and gully blocking. This talk will present data from a five-year, observational-study of CO2 fluxes from eight sites, with four sites sampling different restoration treatments and four sampling bare and least disturbed areas. The results of the analysis reveal that sites with revegetation alongside slope stabilisation were most productive and were the largest net (daylight hours) sinks of CO2. Unrestored, bare sites, while having relatively low gross fluxes of CO2 were the largest net sources of CO2. Revegetation without slope stabilisation took longer (~18 months) to show an impact on CO2 flux in comparison to the sites with slope stabilisation. Binary logistic regression indicated that a ten centimetre increase in water table depth decreases the odds of observing a net CO2 sink, on a given site, by up to 30%. Sites with slope stabilisation were between 5-8x more likely to be net CO2 sinks than the bare sites. Sites without slope stabilisation were only 2-2.3x more likely to be net CO2 sinks compared to the bare sites. The most important conclusion of this research is that revegetation appears to be effective at increasing the likelihood of net CO2 behaviour on degraded, climatically marginal blanket peat, with revegetation alongside slope stabilisation having the greatest impact.

Designed topology and site-selective metal composition in tetranuclear [MM'...M'M] linear complexes.

PubMed

Barrios, Leoní A; Aguilà, David; Roubeau, Olivier; Gamez, Patrick; Ribas-Ariño, Jordi; Teat, Simon J; Aromí, Guillem

2009-10-26

The ligand 1,3-bis[3-oxo-3-(2-hydroxyphenyl)propionyl]benzene (H(4)L), designed to align transition metals into tetranuclear linear molecules, reacts with M(II) salts (M=Ni, Co, Cu) to yield complexes with the expected [MMMM] topology. The novel complexes [Co(4)L(2)(py)(6)] (2; py=pyridine) and [Na(py)(2)][Cu(4)L(2)(py)(4)](ClO(4)) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni(4)L(2)(py)(6)] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu(2)Ni(2)L(2)(py)(6)] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi-independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two-qbit quantum gate.

Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel.

PubMed

Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

2016-01-07

Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially 'clean' strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2(•-) radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO(-)) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems, especially once the influence of both the atomic-scale structure and the presence of oxide are mechanistically better understood.

Active sites of ligand-protected Au{sub 25} nanoparticle catalysts for CO{sub 2} electroreduction to CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alfonso, Dominic R., E-mail: alfonso@netl.doe.gov; Kauffman, Douglas; Matranga, Christopher

2016-05-14

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO{sub 2}) into CO at atomically precise negatively charged Au{sub 25}{sup −} nanoclusters. The studies showed CO{sub 2} conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO{sub 2} reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO{sub 2} reduction catalyst because formationmore » of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO{sub 2} reduction at gold nanocluster catalysts.« less

Superfund Record of Decision Amendment (EPA Region 6): Texarkana Wood Preserving Co. , Texarkana, TX, March 13, 1998

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This decision document presents an amendment to the selected remedial action for the Texarkana Wood Preserving Co. Superfund Site. This amendment fundamentally changes the Record of Decision (ROD) executed by the Regional Administrator on September 25, 1990. This amended remedy will seal and contain soils contaminated with greater than 3 ppm (parts per million) benzo(a)pyrene equivalents, 2450 ppm total poly aromatic hydrocarbons (PAH), 20 ppb (parts per billion) as 2,3,7,8 TCDD equivalents and 150 ppm pentachlorophenol beneath a soil cap.

Siting process for disposal site of low level radiactive waste in Thailand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamkate, P.; Sriyotha, P.; Thiengtrongjit, S.

The radioactive waste in Thailand is composed of low level waste from the application of radioisotopes in medical treatment and industry, the operation of the 2 MW TRIGA Mark III Research Reactor and the production of radioisotopes at OAEP. In addition, the high activity of sealed radiation sources i.e. Cs-137 Co-60 and Ra-226 are also accumulated. Since the volume of treated waste has been gradually increased, the general needs for a repository become apparent. The near surface disposal method has been chosen for this aspect. The feasibility study on the underground disposal site has been done since 1982. The sitemore » selection criteria have been established, consisting of the rejection criteria, the technical performance criteria and the economic criteria. About 50 locations have been picked for consideration and 5 candidate sites have been selected and subsequent investigated. After thoroughly investigation, a definite location in Ratchburi Province, about 180 kilometers southwest of Bangkok, has been selected as the most suitable place for the near surface disposal of radioactive waste in Thailand.« less

Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Complementary phosphorylation sites in the adaptor protein SLP-76 promote synergistic activation of natural killer cells.

PubMed

Kim, Hun Sik; Long, Eric O

2012-07-10

The cytotoxic effects of natural killer (NK) cells and their ability to secrete cytokines require synergistic signals from specific pairs of co-activation receptors, such as CD314 (also known as NKG2D) and CD244 (2B4), which bind to distinct ligands present on target cells. These signals are required to overcome inhibition mediated by the E3 ubiquitin ligase c-Cbl of the guanine nucleotide exchange factor Vav1, which promotes activation of NK cells. Here, we showed that the adaptor protein SLP-76 (Src homology 2 domain-containing leukocyte phosphoprotein of 76 kilodaltons) was required for this synergy and that distinct tyrosine residues in SLP-76 were phosphorylated by each member of a pair of synergistic receptors. Selective phosphorylation of tyrosine 113 or tyrosine 128 in SLP-76 enabled binding of SLP-76 to Vav1. Selective phosphorylation of SLP-76 at these residues was restricted to receptors that stimulated ligand-dependent target cell killing; antibody-dependent stimulation of the Fc receptor CD16 promoted phosphorylation at both sites. Knockdown and reconstitution experiments with SLP-76 mutant proteins showed the distinct role of each tyrosine in the synergistic mobilization of Ca2+, revealing an unexpected degree of selectivity in the phosphorylation of SLP-76 by NK cell co-activation receptors. Together, these data suggest that combined phosphorylation of separate tyrosine residues in SLP-76 forms the basis of synergistic NK cell activation.

Early atmospheric detection of carbon dioxide from carbon capture and storage sites.

PubMed

Pak, Nasrin Mostafavi; Rempillo, Ofelia; Norman, Ann-Lise; Layzell, David B

2016-08-01

The early atmospheric detection of carbon dioxide (CO2) leaks from carbon capture and storage (CCS) sites is important both to inform remediation efforts and to build and maintain public support for CCS in mitigating greenhouse gas emissions. A gas analysis system was developed to assess the origin of plumes of air enriched in CO2, as to whether CO2 is from a CCS site or from the oxidation of carbon compounds. The system measured CO2 and O2 concentrations for different plume samples relative to background air and calculated the gas differential concentration ratio (GDCR = -ΔO2/ΔCO2). The experimental results were in good agreement with theoretical calculations that placed GDCR values for a CO2 leak at 0.21, compared with GDCR values of 1-1.8 for the combustion of carbon compounds. Although some combustion plume samples deviated in GDCR from theoretical, the very low GDCR values associated with plumes from CO2 leaks provided confidence that this technology holds promise in providing a tool for the early detection of CO2 leaks from CCS sites. This work contributes to the development of a cost-effective technology for the early detection of leaks from sites where CO2 has been injected into the subsurface to enhance oil recovery or to permanently store the gas as a strategy for mitigating climate change. Such technology will be important in building public confidence regarding the safety and security of carbon capture and storage sites.

Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C2H2/CO2 and C2H2/CH4 separation performance.

PubMed

Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Qu, Peng; Zhai, Quan-Guo

2018-02-20

A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH 4 (120.6) selectivity among all the reported MOFs at room temperature.

Active chemisorption sites in functionalized ionic liquids for carbon capture.

PubMed

Cui, Guokai; Wang, Jianji; Zhang, Suojiang

2016-07-25

Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined.

Atmospheric fossil fuel CO2 traced by 14CO2 and air quality index pollutant observations in Beijing and Xiamen, China.

PubMed

Niu, Zhenchuan; Zhou, Weijian; Feng, Xue; Feng, Tian; Wu, Shugang; Cheng, Peng; Lu, Xuefeng; Du, Hua; Xiong, Xiaohu; Fu, Yunchong

2018-06-01

Radiocarbon ( 14 C) is the most accurate tracer available for quantifying atmospheric CO 2 derived from fossil fuel (CO 2ff ), but it is expensive and time-consuming to measure. Here, we used common hourly Air Quality Index (AQI) pollutants (AQI, PM 2.5 , PM 10 , and CO) to indirectly trace diurnal CO 2ff variations during certain days at the urban sites in Beijing and Xiamen, China, based on linear relationships between AQI pollutants and CO 2ff traced by 14 C ([Formula: see text]) for semimonthly samples obtained in 2014. We validated these indirectly traced CO 2ff (CO 2ff-in ) concentrations against [Formula: see text] concentrations traced by simultaneous diurnal 14 CO 2 observations. Significant (p < 0.05) strong correlations were observed between each of the separate AQI pollutants and [Formula: see text] for the semimonthly samples. Diurnal variations in CO 2ff traced by each of the AQI pollutants generally showed similar trends to those of [Formula: see text], with high agreement at the sampling site in Beijing and relatively poor agreement at the sampling site in Xiamen. AQI pollutant tracers showed high normalized root-mean-square (NRMS) errors for the summer diurnal samples due to low [Formula: see text] concentrations. After the removal of these summer samples, the NRMS errors for AQI pollutant tracers were in the range of 31.6-64.2%. CO generally showed a high agreement and low NRMS errors among these indirect tracers. Based on these linear relationships, monthly CO 2ff averages at the sampling sites in Beijing and Xiamen were traced using CO concentration as a tracer. The monthly CO 2ff averages at the Beijing site showed a shallow U-type variation. These results indicate that CO can be used to trace CO 2ff variations in Chinese cities with CO 2ff concentrations above 5 ppm.

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts

DOE PAGES

Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander; ...

2017-07-14

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less

The effect of simultaneous substitution on the electronic band structure and thermoelectric properties of Se-doped Co3SnInS2 with the Kagome lattice

NASA Astrophysics Data System (ADS)

Fujioka, Masaya; Shibuya, Taizo; Nakai, Junya; Yoshiyasu, Keigo; Sakai, Yuki; Takano, Yoshihiko; Kamihara, Yoichi; Matoba, Masanori

2014-12-01

The thermoelectric properties and electronic band structures for Se-doped Co3SnInS2 were examined. The parent compound of this material (Co3Sn2S2) has two kinds of Sn sites (Sn1 and Sn2 sites). The density functional theory (DFT) calculations show that the indium substitution at the Sn2 site induces a metallic band structure, on the other hand, a semiconducting band structure is obtained from substitution at the Sn1 site. However, according to the previous reports, since the indium atom prefers to replace the tin atom at the Sn1 site rather than the Sn2 site, the resistivity of Co3SnInS2 shows semiconducting-like behavior. In this study we have demonstrated that metallic behavior and a decrease in resistivity for Se-doped Co3SnInS2 occurs without suppression of the Seebeck coefficient. From the DFT calculations, when the selenium content is above 0.5, the total crystallographic energy shows that a higher indium occupancy at Sn2 site is more stable. Therefore, it is suggested that the selenium doping suppress the site preference for indium substitution. This is one of the possible explanations for the metallic conductivity observed in Se-doped Co3SnInS2

CO2 exchange in the Hudson Bay lowlands: Community characteristics and multispectral reflectance properties

NASA Technical Reports Server (NTRS)

Whiting, Gary J.

1994-01-01

Net ecosystem CO2 exchange was measured during the 1990 growing season (June to August) along a transect starting 10 km inland from James Bay and extending 100 km interior to Kinosheo Lake, Ontario. Sites were chosen in three distinct areas: a coastal fen, an interior fen, and a bog. For the most productive sites in the bog, net daily uptake rates reached a maximum of 2.5 g C-CO2 m(exp -2)/d with an area-weighted exchange of 0.3 g C-CO2 m(exp -2)/d near midsummer. This site was estimated to be a net carbon source of 9 g C-CO2 m(exp -2) to the atmosphere over a 153-day growing season. The interior fen was less productive on a daily basis with a net maximum uptake of 0.5 g C-CO2 m(exp -2)/d and with corresponding area-weighted uptake of 0.1 g C-CO2 m(exp -2)/d during midsummer. Early and late season release of carbon to the atmosphere resulted in a net loss of 21 g C-CO2 m(exp -2) over the growing season from this site. The coastal fen was the most productive site with uptake rates peaking near 1.7 g C-CO2 m(exp -2)/d which corresponded to an area-weighted uptake of 0.8 g C-CO2 m(exp -2)/d during midsummer and an estimated net uptake of 6 g C-CO2 m(exp -2) for the growing season. Associated with net CO2 exchange measurements, multispectral reflectance properties of the sites were measured over the growing season using portable radiometers. These properties were related to exchange rates with the goal of examining the potential for satellite remote sensing to monitor biosphere/atmosphere CO2 exchange in this biome. The normalized difference vegetation index (NDVI) computed from surface reflectance was correlated with net CO2 exchange for all sites with the exception of areas with large proportions of Sphagnum moss cover. These mosses have greater near-infrared reflectance than typical surrounding vegetation and may require special adjustment for regional exchange/remote sensing applications.

Acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts for hydrodeoxygenation process

NASA Astrophysics Data System (ADS)

Lup, A. Ng K.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

2018-03-01

Hydrodeoxygenation is an oxygen removal process that occurs in the presence of hydrogen and catalysts. This study has shown the importance of acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts in having high hydrodeoxygenation activity and selectivity. These properties are required to ensure the catalyst has high affinity for C-O or C=O bonds and the capability for the adsorption and activation of H2 and O-containing compounds. A theoretical framework of temperature programmed desorption technique was also discussed for the quantitative understanding of these properties. By using NH3-TPD, the nature and abundance of acid sites of catalyst can be determined. By using H2-TPD, the nature and abundance of metallic sites can also be determined. The desorption activation energy could also be determined based on the Redhead analysis of TPD spectra with different heating rates.

Integrated Framework for Assessing Impacts of CO₂ Leakage on Groundwater Quality and Monitoring-Network Efficiency: Case Study at a CO₂ Enhanced Oil Recovery Site.

PubMed

Yang, Changbing; Hovorka, Susan D; Treviño, Ramón H; Delgado-Alonso, Jesus

2015-07-21

This study presents a combined use of site characterization, laboratory experiments, single-well push-pull tests (PPTs), and reactive transport modeling to assess potential impacts of CO2 leakage on groundwater quality and leakage-detection ability of a groundwater monitoring network (GMN) in a potable aquifer at a CO2 enhanced oil recovery (CO2 EOR) site. Site characterization indicates that failures of plugged and abandoned wells are possible CO2 leakage pathways. Groundwater chemistry in the shallow aquifer is dominated mainly by silicate mineral weathering, and no CO2 leakage signals have been detected in the shallow aquifer. Results of the laboratory experiments and the field test show no obvious damage to groundwater chemistry should CO2 leakage occur and further were confirmed with a regional-scale reactive transport model (RSRTM) that was built upon the batch experiments and validated with the single-well PPT. Results of the RSRTM indicate that dissolved CO2 as an indicator for CO2 leakage detection works better than dissolved inorganic carbon, pH, and alkalinity at the CO2 EOR site. The detection ability of a GMN was assessed with monitoring efficiency, depending on various factors, including the natural hydraulic gradient, the leakage rate, the number of monitoring wells, the aquifer heterogeneity, and the time for a CO2 plume traveling to the monitoring well.

Structure sensitivity in the kinetics and the dynamics of CO oxidation over stepped Pd(335) studied by the molecular beam infrared chemiluminescence technique: Determination of working sites during the steady-state reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uetsuka, H.; Watanabe, K.; Kimpara, H.

Kinetics and dynamics of CO oxidation have been studied on a stepped Pd(335) surface at a steady-state condition and compared with those on flat Pd(111). The infrared (IR) chemiluminescence technique was applied to determine where the active catalytic sites are on the Pd(335) surface. Since the vibrational energy state of the product CO{sub 2} is sensitive to the structures of the reaction sites on Pd surfaces, information about the working reaction sites during the steady-state CO oxidation can be obtained from the IR emission spectra of the product CO{sub 2}. The production rate of CO{sub 2} was higher on Pd(335)more » than on Pd(111), indicating that the steps on the surface enhance the catalytic activity for Co oxidation under the steady-state condition. However, the rate data do not necessarily show the real active sites for the CO + O recombination reaction. At a surface temperature of 850 K, the vibrational Boltzmann temperature (T{sub v}) of the product CO{sub 2} on Pd(335) was quite different from (much lower than) that on Pd(111), although the Pd(335) surface has four-atom wide (111) terraces. The lower T{sub v} value on Pd(335) was similar to that on Pd(110)(1 x 1), indicating that a relatively linear activated CO{sub 2} complex was formed. Therefore, during the steady-state CO oxidation on Pd(335), the reaction does not take place on the (111) terrace sites, but mostly on the step sites at 850 K. On the contrary, as the CO coverage increased at a lower surface temperature and at a high CO/O{sub 2} ratio, the T{sub v} values on Pd(335) tend to approach those on Pd(111), indicating that the contribution of the active sites on the steps is decreased and the working reaction sites shift to the (111) terrace sites.« less

A single-ligand ultra-microporous MOF for precombustion CO2 capture and hydrogen purification

PubMed Central

Nandi, Shyamapada; De Luna, Phil; Daff, Thomas D.; Rother, Jens; Liu, Ming; Buchanan, William; Hawari, Ayman I.; Woo, Tom K.; Vaidhyanathan, Ramanathan

2015-01-01

Metal organic frameworks (MOFs) built from a single small ligand typically have high stability, are rigid, and have syntheses that are often simple and easily scalable. However, they are normally ultra-microporous and do not have large surface areas amenable to gas separation applications. We report an ultra-microporous (3.5 and 4.8 Å pores) Ni-(4-pyridylcarboxylate)2 with a cubic framework that exhibits exceptionally high CO2/H2 selectivities (285 for 20:80 and 230 for 40:60 mixtures at 10 bar, 40°C) and working capacities (3.95 mmol/g), making it suitable for hydrogen purification under typical precombustion CO2 capture conditions (1- to 10-bar pressure swing). It exhibits facile CO2 adsorption-desorption cycling and has CO2 self-diffusivities of ~3 × 10−9 m2/s, which is two orders higher than that of zeolite 13X and comparable to other top-performing MOFs for this application. Simulations reveal a high density of binding sites that allow for favorable CO2-CO2 interactions and large cooperative binding energies. Ultra-micropores generated by a small ligand ensures hydrolytic, hydrostatic stabilities, shelf life, and stability toward humid gas streams. PMID:26824055

Natural analogues for CO2 storage sites - analysis of a global dataset

NASA Astrophysics Data System (ADS)

Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, R. Stuart

2013-04-01

Carbon Capture and Storage is the only industrial scale technology currently available to reduce CO2 emissions from fossil-fuelled power plants and large industrial source to the atmosphere and thus mitigate climate change. CO2 is captured at the source and transported to subsurface storage sites, such as depleted oil and gas fields or saline aquifers. In order to have an effect on emissions and to be considered safe it is crucial that the amount of CO2 leaking from storage sites to shallow aquifers or the surface remains very low (<1% over 1000 years). Some process that influence the safety of a reservoir, such as CO2-rock-brine interactions, can be studied using experiments on both laboratory and field-scale. However, long-term processes such as the development of leakage pathways can only be understood by either predictive modelling or by studying natural CO2 reservoirs as analogues for long term CO2 storage sites. Natural CO2 reservoirs have similar geological trapping mechanisms as anticipated for CO2 storage sites and often have held CO2 for a geological period of time (millions of years) without any indication for leakage. Yet, migration of CO2 from reservoirs to the surface is also common and evidenced by gas seeps such as springs and soil degassing. We have compiled and analysed a dataset comprising of more than 50 natural CO2 reservoirs from different settings all around the globe to provide an overview of the factors that are important for the retention of CO2 in the subsurface and what processes lead to leakage of CO2 from the reservoir. Initial results indicate that if the reservoir is found to be leaking, CO2 migration is along faults and not through caprock layers. This indicates that faults act as fluid pathways and play an important role when characterizing a storage site. Additionally, it appears that overpressure of the overburden and the state of CO2 in the reservoir influence the likelihood of migration and hence the safety of a reservoir.

3D-QSAR comparative molecular field analysis on opioid receptor antagonists: pooling data from different studies.

PubMed

Peng, Youyi; Keenan, Susan M; Zhang, Qiang; Kholodovych, Vladyslav; Welsh, William J

2005-03-10

Three-dimensional quantitative structure-activity relationship (3D-QSAR) models were constructed using comparative molecular field analysis (CoMFA) on a series of opioid receptor antagonists. To obtain statistically significant and robust CoMFA models, a sizable data set of naltrindole and naltrexone analogues was assembled by pooling biological and structural data from independent studies. A process of "leave one data set out", similar to the traditional "leave one out" cross-validation procedure employed in partial least squares (PLS) analysis, was utilized to study the feasibility of pooling data in the present case. These studies indicate that our approach yields statistically significant and highly predictive CoMFA models from the pooled data set of delta, mu, and kappa opioid receptor antagonists. All models showed excellent internal predictability and self-consistency: q(2) = 0.69/r(2) = 0.91 (delta), q(2) = 0.67/r(2) = 0.92 (mu), and q(2) = 0.60/r(2) = 0.96 (kappa). The CoMFA models were further validated using two separate test sets: one test set was selected randomly from the pooled data set, while the other test set was retrieved from other published sources. The overall excellent agreement between CoMFA-predicted and experimental binding affinities for a structurally diverse array of ligands across all three opioid receptor subtypes gives testimony to the superb predictive power of these models. CoMFA field analysis demonstrated that the variations in binding affinity of opioid antagonists are dominated by steric rather than electrostatic interactions with the three opioid receptor binding sites. The CoMFA steric-electrostatic contour maps corresponding to the delta, mu, and kappa opioid receptor subtypes reflected the characteristic similarities and differences in the familiar "message-address" concept of opioid receptor ligands. Structural modifications to increase selectivity for the delta over mu and kappa opioid receptors have been predicted on the basis of the CoMFA contour maps. The structure-activity relationships (SARs) together with the CoMFA models should find utility for the rational design of subtype-selective opioid receptor antagonists.

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew

Despite the numerous studies on changes within the reservoir following CO2 injection and the effects of CO2 release into overlying aquifers, little or no literature is available on the effect of CO2 release on rock between the storage reservoirs and subsurface. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in this intermediate zone. After rocks reacted with CO2, liquid analysis showed an increase of major elements (e.g., Ca, and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower concentrations were observed in N2 controls. In experimentsmore » with As/Cd and/or organic spikes, representing potential contaminants in the CO2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less

Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mason, JA; Sumida, K; Herm, ZR

Two representative metal-organic frameworks, Zn4O(BTB)(2)(BTB3- = 1,3,5-benzenetribenzoate; MOF-177) and Mg-2(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temperature swing adsorption (TSA). Low-pressure single-component CO2 and N-2 adsorption isotherms were measured every 10 degrees C from 20 to 200 degrees C, allowing the performance of each material to be analyzed precisely. In order to gain a more complete understanding of the separation phenomena and the thermodynamics of CO2 adsorption, the isotherms were analyzed using a variety of methods. With regard to the isosteric heat of CO2 adsorption, Mg-2(dobdc) exhibits anmore » abrupt drop at loadings approaching the saturation of the Mg2+ sites, which has significant implications for regeneration in different industrial applications. The CO2/N-2 selectivities were calculated using ideal adsorbed solution theory (IAST) for MOF-177, Mg-2(dobdc), and zeolite NaX, and working capacities were estimated using a simplified TSA model. Significantly, MOF-177 fails to exhibit a positive working capacity even at regeneration temperatures as high as 200 degrees C, while Mg-2(dobdc) reaches a working capacity of 17.6 wt% at this temperature. Breakthrough simulations were also performed for the three materials, demonstrating the superior performance of Mg-2(dobdc) over MOF-177 and zeolite NaX. These results show that the presence of strong CO2 adsorption sites is essential for a metal-organic framework to be of utility in post-combustion CO2 capture via a TSA process, and present a methodology for the evaluation of new metal-organic frameworks via analysis of single-component gas adsorption isotherms.« less

The Role of Subsurface Properties on Transport of Water and Trace Gases: 1D Simulations at Selected Mars Landing Sites.

NASA Astrophysics Data System (ADS)

Karatekin, O.; Gloesener, E.; Dehant, V. M. A.

2017-12-01

In this work, water ice stability and water vapour transport through porous martian subsurface are studied using a 1D diffusive model. The role of adsorption on water transfer in martian conditions is investigated as well as the range of parameters that have the largest effect on gas transport. In addition, adsorption kinetics is considered to examine its influence on the water vapor exchange between the subsurface and the atmosphere. As methane has been detected in the martian atmosphere, the subsurface model is then used to study methane diffusion in the CH4/CO2/H2O system from variable depths under the surface. The results of subsurface gas transport at selected locations/landing sites are shown and implications for present/future observations are discussed.

Radiocarbon-depleted CO2 evidence for fuel biodegradation at the Naval Air Station North Island (USA) fuel farm site.

PubMed

Boyd, Thomas J; Pound, Michael J; Lohr, Daniel; Coffin, Richard B

2013-05-01

Dissolved CO(2) radiocarbon and stable carbon isotope ratios were measured in groundwater from a fuel contaminated site at the North Island Naval Air Station in San Diego, CA (USA). A background groundwater sampling well and 16 wells in the underground fuel contamination zone were evaluated. For each sample, a two end-member isotopic mixing model was used to determine the fraction of CO(2) derived from fossil fuel. The CO(2) fraction from fossil sources ranged from 8 to 93% at the fuel contaminated site, while stable carbon isotope values ranged from -14 to +5‰VPDB. Wells associated with highest historical and contemporary fuel contamination showed the highest fraction of CO(2) derived from petroleum (fossil) sources. Stable carbon isotope ratios indicated sub-regions on-site with recycled CO(2) (δ(13)CO(2) as high as +5‰VPDB) - most likely resulting from methanogenesis. Ancillary measurements (pH and cations) were used to determine that no fossil CaCO(3), for instance limestone, biased the analytical conclusions. Radiocarbon analysis is verified as a viable and definitive technique for confirming fossil hydrocarbon conversion to CO(2) (complete oxidation) at hydrocarbon-contaminated groundwater sites. The technique should also be very useful for assessing the efficacy of engineered remediation efforts and by using CO(2) production rates, contaminant mass conversion over time and per unit volume.

Understanding the behavior of carbon dioxide and surface energy fluxes in semiarid Salt Lake Valley, Utah, USA

NASA Astrophysics Data System (ADS)

Ramamurthy, Prathap

This dissertation reports the findings from the Salt Lake Valley flux study. The Salt Lake Valley flux study was designed to improve our understanding of the complex land-atmosphere interactions in urban areas. The flux study used the eddy covariance technique to quantify carbon dioxide and surface energy budget in the semiarid Salt Lake Valley. Apart from quantifying fluxes, the study has also added new insight into the nature of turbulent scalar transport in urban areas and has addressed some of the complications in using Eddy Covariance technique in urban areas. As part of this experiment, eddy fluxes of CO2 and surface energy fluxes were measured at two sites, with distinct urban landforms; One site was located in a suburban neighborhood with substantial vegetative cover, prototypical of many residential neighborhoods in the valley. The other CO2 site was in a preurban surrounding that resembled the Salt Lake Valley before it was urbanized. The two sites were intentionally chosen to illustrate the impact of urbanization on CO 2 and surface energy flux cycles. Results indicate that the suburban site acted as a sink of CO2 during the midday period due to photosynthesis and acted as a source of CO2 during the evening and nighttime periods. The vegetative cover around the suburban site also had a significant impact on the surface energy fluxes. Contribution from latent heat flux was substantially high at the suburban site during the summer months compared to sensible heat. The turbulence investigation found that the general behavior of turbulence was very much influenced by local factors and the statistics did not always obey Monin-Obukhov Similarity parameters. This investigation also found that the scalar (co)spectra observed at the suburban site were characterized by multiple peaks and were different compared to (co)spectra reported over forest and crop canopies. The study also observed multiscale CO2 transport at the suburban site during the convective period. While the suburban site acted as a net sink of CO2 during the midday periods, CO2 was transported positively at lower frequencies. Also, during the evening transition period, when the site switched from a sink of CO2 to a source, the net upward transport of CO2 was cancelled by the net downward transport of CO2. This balance caused the total net transport reduce to zero. Overall this research, apart from characterizing the behavior of scalar fluxes at a suburban site in a semiarid desert city has also added some valuable insight on the complex nature of urban scalar transport.

Greenhouse gas emissions from rewetted bog peat extraction sites and a Sphagnum cultivation site in Northwest Germany

NASA Astrophysics Data System (ADS)

Beyer, C.; Höper, H.

2014-03-01

During the last three decades, an increasing area of drained peatlands was rewetted. This was done with the objective to convert these sites from sources back to sinks or, at least, to much smaller sources of greenhouse gases (GHG). However, available data is still scarce, especially on the long-term climatic effects of rewetting of temperate bogs. Moreover, first field trials are established for Sphagnum cultivating (paludiculture) on wet bog sites and an assessment of the climate impact of such measures has not been studied yet. We conducted a field study on the exchange of carbon dioxide, methane and nitrous oxide at three rewetted sites with a gradient from dry to wet conditions and at a Sphagnum cultivation site in NW Germany over more than two years. Gas fluxes were measured using transparent and opaque closed chambers. The ecosystem respiration (CO2) and the net ecosystem exchange (CO2) were modelled in high time resolution using automatically monitored climate data. Measured and modelled values fit very well together (R2 between 0.88 and 0.98). Annually cumulated gas flux rates, net ecosystem carbon balances (NECB) and global warming potential (GWP) balances were determined. The annual net ecosystem exchange (CO2) varied strongly at the rewetted sites (from -201.7 ± 126.8 to 29.7 ± 112.7 g CO2-C m-2 a-1) due to different weather conditions, water level and vegetation. The Sphagnum cultivation site was a sink of CO2 (-118.8 ± 48.1 and -78.6 ± 39.8 g CO2-C m-2 a-1). The yearly CH4 balances ranged between 16.2 ± 2.2 and 24.2 ± 5.0 g CH4-C m-2 a-1 at two inundated sites, while one rewetted site with a comparatively low water level and the Sphagnum farming site show CH4 fluxes close to zero. The net N2O fluxes were low and not significantly different between the four sites. The annual NECB at the rewetted sites was between -183.8 ± 126.9 and 51.6 ± 112.8 g CO2-C m-2 a-1 and at the Sphagnum cultivating site -114.1 ± 48.1 and -75.3 ± 39.8 g CO2-C m-2 a-1. The yearly GWP100 balances ranged from -280.5 ± 465.2 to 644.5 ± 413.6 g CO2-eq. m-2 a-1 at the rewetted sites. In contrast, the Sphagnum farming site had a cooling impact on the climate in both years (-356.8 ± 176.5 and -234.9 ± 145.9 g CO2-C m-2 a-1). If the exported carbon through the harvest of the Sphagnum biomass and the additional CO2 emission from the decay of the organic material is considered, the NECB and GWP100 balances are near neutral. Peat mining sites are likely to become net carbon sinks and a peat accumulating ("growing") peatland within 30 years after rewetting, but the GWP100 balance may still be positive. A recommended measure for rewetting is to achieve a water level of a few centimetres below ground surface. Sphagnum farming is a climate friendly alternative to conventional commercial use of bogs. A year round constant water level of a few centimetres below ground level should be maintained.

Diurnal Characteristics of Surface-Level O3 and Other Trace Gases in New England

NASA Astrophysics Data System (ADS)

Talbot, R.; Mao, H.; Sive, B.

2003-12-01

We use data from air quality monitoring sites operated by the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) program to examine the diurnal characteristics of O3, CO, CO2 and selected volatile organic compounds (VOCs) in the New England atmosphere. Throughout the year a nocturnal inversion forms several hundred meters above the surface on 25% of the days in winter with its frequency of occurrence increasing to 50% in summer. Below the inversion O3 is typically depleted to zero while other gases including CO2, alkanes and alkenes exhibit several-fold enhancements due to local emission sources. The daily time period with O3 < 5 ppbv varies from < 0.5 to 21 hours, with a mean of 3.5 hours. Typically the depletion intervals are shortest in summer and last the longest in winter. The rates of nighttime depletion and daytime replenishment of O3 are very similar, ranging from a few ppbv hr-1 to 25 ppbv hr-1. Due to the rural location of the AIRMAP sites, it appears that the depletion is mainly due to dry deposition with an occasional contribution of titration by NO. The relative enhancements of CO2 and VOCs relative to urban tracers such as C2HCl3 and C2Cl4, which have minimal local sources, provides information on the magnitude and nature of natural and anthropogenic sources.

Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

PubMed

Wang, Hui-Fang; Liu, Zhi-Pan

2008-08-20

Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

Positive selection on human gamete-recognition genes

PubMed Central

Stover, Daryn A.; Guerra, Vanessa; Mozaffari, Sahar V.; Ober, Carole; Mugal, Carina F.; Kaj, Ingemar

2018-01-01

Coevolution of genes that encode interacting proteins expressed on the surfaces of sperm and eggs can lead to variation in reproductive compatibility between mates and reproductive isolation between members of different species. Previous studies in mice and other mammals have focused in particular on evidence for positive or diversifying selection that shapes the evolution of genes that encode sperm-binding proteins expressed in the egg coat or zona pellucida (ZP). By fitting phylogenetic models of codon evolution to data from the 1000 Genomes Project, we identified candidate sites evolving under diversifying selection in the human genes ZP3 and ZP2. We also identified one candidate site under positive selection in C4BPA, which encodes a repetitive protein similar to the mouse protein ZP3R that is expressed in the sperm head and binds to the ZP at fertilization. Results from several additional analyses that applied population genetic models to the same data were consistent with the hypothesis of selection on those candidate sites leading to coevolution of sperm- and egg-expressed genes. By contrast, we found no candidate sites under selection in a fourth gene (ZP1) that encodes an egg coat structural protein not directly involved in sperm binding. Finally, we found that two of the candidate sites (in C4BPA and ZP2) were correlated with variation in family size and birth rate among Hutterite couples, and those two candidate sites were also in linkage disequilibrium in the same Hutterite study population. All of these lines of evidence are consistent with predictions from a previously proposed hypothesis of balancing selection on epistatic interactions between C4BPA and ZP3 at fertilization that lead to the evolution of co-adapted allele pairs. Such patterns also suggest specific molecular traits that may be associated with both natural reproductive variation and clinical infertility. PMID:29340252

High-Performance Carbon Dioxide Electrocatalytic Reduction by Easily Fabricated Large-Scale Silver Nanowire Arrays.

PubMed

Luan, Chuhao; Shao, Yang; Lu, Qi; Gao, Shenghan; Huang, Kai; Wu, Hui; Yao, Kefu

2018-05-30

An efficient and selective catalyst is in urgent need for carbon dioxide electroreduction and silver is one of the promising candidates with affordable costs. Here we fabricated large-scale vertically standing Ag nanowire arrays with high crystallinity and electrical conductivity as carbon dioxide electroreduction catalysts by a simple nanomolding method that was usually considered not feasible for metallic crystalline materials. A great enhancement of current densities and selectivity for CO at moderate potentials was achieved. The current density for CO ( j co ) of Ag nanowire array with 200 nm in diameter was more than 2500 times larger than that of Ag foil at an overpotential of 0.49 V with an efficiency over 90%. The origin of enhanced performances are attributed to greatly increased electrochemically active surface area (ECSA) and higher intrinsic activity compared to those of polycrystalline Ag foil. More low-coordinated sites on the nanowires which can stabilize the CO 2 intermediate better are responsible for the high intrinsic activity. In addition, the impact of surface morphology that induces limited mass transportation on reaction selectivity and efficiency of nanowire arrays with different diameters was also discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2.

PubMed

Ju, Wen; Bagger, Alexander; Hao, Guang-Ping; Varela, Ana Sofia; Sinev, Ilya; Bon, Volodymyr; Roldan Cuenya, Beatriz; Kaskel, Stefan; Rossmeisl, Jan; Strasser, Peter

2017-10-16

Direct electrochemical reduction of CO 2 to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO 2 -consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO 2 to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N x moieties (M = Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N x moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N x moieties and it provides predictive guidelines for the rational design of selective carbon-based CO 2 reduction catalysts.Inexpensive and selective electrocatalysts for CO 2 reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO 2 to CO conversion.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

NASA Astrophysics Data System (ADS)

Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

2017-11-01

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

From Site Characterization through Safe and Successful CO2 Injection Operation to Post-injection Monitoring and Site Closure - Closing the Full Life Cycle Research at the Ketzin Pilot Site, Germany

NASA Astrophysics Data System (ADS)

Liebscher, Axel

2017-04-01

Initiated in 2004, the Ketzin pilot site near Berlin, Germany, was the first European onshore storage project for research and development on geological CO2 storage. After comprehensive site characterization the site infrastructure was build comprising three deep wells and the injection facility including pumps and storage tanks. The operational CO2 injection period started in June 2008 and ended in August 2013 when the site entered the post-injection closure period. During these five years, a total amount of 67 kt of CO2 was safely injected into an Upper Triassic saline sandstone aquifer at a depth of 630 m - 650 m. In fall 2013, the first observation well was partially plugged in the reservoir section with CO2 resistant cement; full abandonment of this well finished in 2015 after roughly 2 years of cement plug monitoring. Abandonment of the remaining wells will be finished by summer 2017 and hand-over of liability to the competent authority is scheduled for end of 2017. The CO2 injected was mainly of food grade quality (purity > 99.9%). In addition, 1.5 kt of CO2 from the oxyfuel pilot capture facility "Schwarze Pumpe" (purity > 99.7%) was injected in 2011. The injection period terminated with a CO2-N2 co-injection experiment of 650 t of a 95% CO2/5% N2 mixture in summer 2013 to study the effects of impurities in the CO2 stream on the injection operation. During regular operation, the CO2 was pre-heated on-site to 40°C prior to injection to ensure a single-phase injection process and avoid any phase transition or transient states within the injection facility or the reservoir. Between March and July 2013, just prior to the CO2-N2 co-injection experiment, the injection temperature was stepwise decreased down to 10°C within a "cold-injection" experiment to study the effects of two-phase injection conditions. During injection operation, the combination of different geochemical and geophysical monitoring methods enabled detection and mapping of the spatial and temporal in-reservoir behaviour of the injected CO2 even for small quantities. After the cessation of CO2 injection, post-injection monitoring continues and is guided by the three high-level criteria set out in the EU Directive for transfer of liability: i) observed behaviour of the injected CO2 conforms to the modelled behaviour, ii) no detectable leakage, and iii) site is evolving towards a situation of long-term stability. In addition, two further field experiments have been performed since end of injection. A CO2 back-production experiment was run in autumn 2014 to study the physicochemical properties of the back-produced CO2 as well as the pressure response of the reservoir. From October 2015 to January 2016, a brine injection experiment aimed at studying the imbibition process and residual gas saturation. Just prior to final well abandonment, drilling of two sidetracks in one of the wells is scheduled for summer 2017 to recover unique core samples from reservoir and cap rocks that reflect 9 years of in-situ CO2 exposure and will provide first-hand information on CO2-triggered mineralogical, mechanical and petrophysical rock property changes.

Remaining gaps for "safe" CO2 storage: the INGV CO2GAPS vision of "learning by doing" monitoring geogas leakage, reservoirs contamination/mixing and induced/triggered seismicity

NASA Astrophysics Data System (ADS)

Quattrocchi, F.; Vinciguerra, S.; Chiarabba, C.; Boschi, E.; Anselmi, M.; Burrato, P.; Buttinelli, M.; Cantucci, B.; Cinti, D.; Galli, G.; Improta, L.; Nazzari, M.; Pischiutta, M.; Pizzino, L.; Procesi, M.; Rovelli, A.; Sciarra, A.; Voltattorni, N.

2012-12-01

The CO2GAPS project proposed by INGV is intended to build up an European Proposal for a new kind of research strategy in the field of the geogas storage. Aim of the project would be to fill such key GAPS concerning the main risks associated to CO2 storage and their implications on the entire Carbon Capture and Storage (CCS) process, which are: i) the geogas leakage both in soils and shallow aquifers, up to indoor seepage; ii) the reservoirs contamination/mixing by hydrocarbons and heavy metals; iii) induced or triggered seismicity and microseismicity, especially for seismogenic blind faults. In order to consider such risks and make the CCS public acceptance easier, a new kind of research approach should be performed by: i) a better multi-disciplinary and "site specific" risk assessment; ii) the development of more reliable multi-disciplinary monitoring protocols. In this view robust pre-injection base-lines (seismicity and degassing) as well as identification and discrimination criteria for potential anomalies are mandatory. CO2 injection dynamic modelling presently not consider reservoirs geomechanical properties during reactive mass-transport large scale simulations. Complex simulations of the contemporaneous physic-chemical processes involving CO2-rich plumes which move, react and help to crack the reservoir rocks are not totally performed. These activities should not be accomplished only by the oil-gas/electric companies, since the experienced know-how should be shared among the CCS industrial operators and research institutions, with the governments support and overview, also flanked by a transparent and "peer reviewed" scientific popularization process. In this context, a preliminary and reliable 3D modelling of the entire "storage complex" as defined by the European Directive 31/2009 is strictly necessary, taking into account the above mentioned geological, geochemical and geophysical risks. New scientific results could also highlighting such opportunities recently shown by strategic researches on the synergies between the use of underground space (e.g. CH4, CO2 storage and deep geothermics) for energetic supplying purposes. The CO2GAPS approach would merge together geomechanical and geochemical data with seismic velocity and anisotropy properties of the crust, induced seismicity data, gravimetry, EM techniques, and "early alarm" procedures for leakage/cracks detection in shallow geo-spheres (e.g. abandoned wells, naturally seismic and degassing zones). Moreover, a full merging of those data is necessary for a reliable 3D-Earth modelling and the subsequent reactive transport simulations. CO2GAPS vision would apply and verify these issues working on several European selected sites, taking also into account complex systems such as "inland" active faulted blocks close to potential off-shore CO2 storage sites, ECBM faulted prone-areas, "inland" injection test site and CO2 natural faulted analogues. The purpose of these activities focus on the study of long-term fate of stored CO2, leakage mechanisms through the cap-rock and/or abandoned wells, cement wells reactivity, as well as the effects of impurities in the CO2 streams, their removal costs, the use of tracers and the role of biota.

MOF-74 as an Efficient Catalyst for the Low-Temperature Selective Catalytic Reduction of NOx with NH3.

PubMed

Jiang, Haoxi; Wang, Qianyun; Wang, Huiqin; Chen, Yifei; Zhang, Minhua

2016-10-12

In this work, Mn-MOF-74 with hollow spherical structure and Co-MOF-74 with petal-like shape have been prepared successfully via the hydrothermal method. The catalysts were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry-mass spectrum analysis (TG-MS), N 2 adsorption/desorption, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). It is found that MOF-74(Mn, Co) exhibits the capability for selective catalytic reduction (SCR) of NO x at low temperatures. Both experimental (temperature-programmed desorption, TPD) and computational methods have shown that Co-MOF-74 and Mn-MOF-74 owned high adsorption and activation abilities for NO and NH 3 . The catalytic activities of Mn-MOF-74 and Co-MOF-74 for low-temperature denitrification (deNO x ) in the presence of NH 3 were 99% at 220 °C and 70% at 210 °C, respectively. It is found that the coordinatively unsaturated metal sites (CUSs) in M-MOF-74 (M = Mn and Co) played important roles in SCR reaction. M-MOF-74 (M = Mn and Co), especially Mn-MOF-74, showed excellent catalytic performance for low-temperature SCR. In addition, in the reaction process, NO conversion on Mn-MOF-74 decreased with the introduction of H 2 O and SO 2 and almost recovered when gas was cut off. However, for Co-MOF-74, SO 2 almost has no effect on the catalytic activity. This work showed that MOF-74 could be used prospectively as deNO x catalyst.

Structural characterization of framework–gas interactions in the metal–organic framework Co 2 (dobdc) by in situ single-crystal X-ray diffraction

DOE PAGES

Gonzalez, Miguel I.; Mason, Jarad A.; Bloch, Eric D.; ...

2017-04-19

The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4, N 2, O 2, Ar, and P 4 adsorption in Co2(dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(II) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(II) sites in the framework that no analogous molecular structures exist,more » demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH 4 and Co–Ar interactions observed in Co 2(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH 4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(II) sites in Co 2(dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol –1 (for Ar). Moreover, the structures of Co 2(dobdc)·3.8N 2, Co 2(dobdc)·5.9O 2, and Co 2(dobdc)·2.0Ar reveal the location of secondary (N 2, O 2, and Ar) and tertiary (O 2) binding sites in Co 2(dobdc), while high-pressure CO 2, CO, CH 4, N 2, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.« less

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

Synthesis of 2-Butanol by Selective Hydrogenolysis of 1,4-Anhydroerythritol over Molybdenum Oxide-Modified Rhodium-Supported Silica.

PubMed

Arai, Takahiro; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2016-07-07

Rh-MoOx /SiO2 (Mo/Rh=0.13) is an effective catalyst for the hydrogenolysis of 1,4-anhydroerythritol (1,4-AHERY) and provides 2-BuOH in high yield of 51 %. This is the first report of the production of 2-BuOH from 1,4-AHERY by hydrogenolysis. 1,4-AHERY was more suitable as a starting material than erythritol because the 2-BuOH yield from erythritol was low (34 %). Based on the kinetics and comparison of reactivities of the related compounds using Rh-MoOx /SiO2 and Rh/SiO2 catalysts, the modification of Rh/SiO2 with MoOx leads to the high activity and high selectivity to 2-BuOH because of the generation of reactive hydride species and the strong adsorption of 1,4-AHERY on MoOx species. The reaction proceeds by main two routes, (I) the combination of single C-O hydrogenolysis with the desorption of intermediates, a usual route in hydrogenolysis, and (II) multiple C-O hydrogenolysis without the desorption of intermediates from the active site, and the reaction mechanism for Route (II) is proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Early atmospheric detection of carbon dioxide from carbon capture and storage sites

PubMed Central

Pak, Nasrin Mostafavi; Rempillo, Ofelia; Norman, Ann-Lise; Layzell, David B.

2016-01-01

ABSTRACT The early atmospheric detection of carbon dioxide (CO2) leaks from carbon capture and storage (CCS) sites is important both to inform remediation efforts and to build and maintain public support for CCS in mitigating greenhouse gas emissions. A gas analysis system was developed to assess the origin of plumes of air enriched in CO2, as to whether CO2 is from a CCS site or from the oxidation of carbon compounds. The system measured CO2 and O2 concentrations for different plume samples relative to background air and calculated the gas differential concentration ratio (GDCR = −ΔO2/ΔCO2). The experimental results were in good agreement with theoretical calculations that placed GDCR values for a CO2 leak at 0.21, compared with GDCR values of 1–1.8 for the combustion of carbon compounds. Although some combustion plume samples deviated in GDCR from theoretical, the very low GDCR values associated with plumes from CO2 leaks provided confidence that this technology holds promise in providing a tool for the early detection of CO2 leaks from CCS sites.  Implications: This work contributes to the development of a cost-effective technology for the early detection of leaks from sites where CO2 has been injected into the subsurface to enhance oil recovery or to permanently store the gas as a strategy for mitigating climate change. Such technology will be important in building public confidence regarding the safety and security of carbon capture and storage sites. PMID:27111469

Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

PubMed

Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

2014-07-17

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

Structural Basis for Certain Naturally Occurring Bioflavonoids to Function as Reducing Co-Substrates of Cyclooxygenase I and II

PubMed Central

Zhu, Bao Ting

2010-01-01

Background Recent studies showed that some of the dietary bioflavonoids can strongly stimulate the catalytic activity of cyclooxygenase (COX) I and II in vitro and in vivo, presumably by facilitating enzyme re-activation. In this study, we sought to understand the structural basis of COX activation by these dietary compounds. Methodology/Principal Findings A combination of molecular modeling studies, biochemical analysis and site-directed mutagenesis assay was used as research tools. Three-dimensional quantitative structure-activity relationship analysis (QSAR/CoMFA) predicted that the ability of bioflavonoids to activate COX I and II depends heavily on their B-ring structure, a moiety known to be associated with strong antioxidant ability. Using the homology modeling and docking approaches, we identified the peroxidase active site of COX I and II as the binding site for bioflavonoids. Upon binding to this site, bioflavonoid can directly interact with hematin of the COX enzyme and facilitate the electron transfer from bioflavonoid to hematin. The docking results were verified by biochemical analysis, which reveals that when the cyclooxygenase activity of COXs is inhibited by covalent modification, myricetin can still stimulate the conversion of PGG2 to PGE2, a reaction selectively catalyzed by the peroxidase activity. Using the site-directed mutagenesis analysis, we confirmed that Q189 at the peroxidase site of COX II is essential for bioflavonoids to bind and re-activate its catalytic activity. Conclusions/Significance These findings provide the structural basis for bioflavonoids to function as high-affinity reducing co-substrates of COXs through binding to the peroxidase active site, facilitating electron transfer and enzyme re-activation. PMID:20808785

Atomic origin of the spin-polarization of the Co2FeAl Heusler compound

NASA Astrophysics Data System (ADS)

Liang, Jaw-Yeu; Lam, Tu-Ngoc; Lin, Yan-Cheng; Chang, Shu-Jui; Lin, Hong-Ji; Tseng, Yuan-Chieh

2016-02-01

Using synchrotron x-ray techniques, we studied the Co2FeAl spin-polarization state that generates the half-metallicity of the compound during an A2 (low-spin)  →  B2 (high-spin) phase transition. Given the advantage of element specificity of x-ray techniques, we could fingerprint the structural and magnetic cross-reactions between Co and Fe within a complex Co2FeAl structure deposited on a MgO (0 0 1) substrate. X-ray diffraction and extended x-ray absorption fine structure investigations determined that the Co atoms preferably populate the (1/4,1/4,1/4) and (3/4,3/4,3/4) sites during the development of the B2 phase. X-ray magnetic spectroscopy showed that although the two magnetic elements were ferromagnetically coupled, they interacted in a competing manner via a charge-transfer effect, which enhanced Co spin polarization at the expense of Fe spin polarization during the phase transition. This means that the spin-polarization of Co2FeAl was electronically dominated by Fe in A2 whereas the charge transfer turned the dominance to Co upon B2 formation. Helicity-dependent x-ray absorption spectra also revealed that only the minority state of Co/Fe was involved in the charge-transfer effect whereas the majority state was independent of it. Despite an overall increase of Co2FeAl magnetization, the charge-transfer effect created an undesired trade-off during the Co-Fe exchange interactions, because of the presence of twice as many X sites (Co) as Y sites (Fe) in the Heusler X 2 YZ formula. This suggests that the spin-polarization of Co2FeAl is unfortunately regulated by compromising the enhanced X (Co) sites and the suppressed Y (Fe) sites, irrespective of the development of the previously known high-spin-polarization phase of B2. This finding provides a possible cause for the limited half-metallicity of Co2FeAl discovered recently. Electronic tuning between the X and Y sites is necessary to further increase the spin-polarization, and likely the half-metallicity as well, of the compound.

DFT studies on H 2O adsorption and its effect on CO oxidation over spinel Co 3O 4 (110) surface

NASA Astrophysics Data System (ADS)

Xu, Xiang Lan; Li, Jun Qian

2011-12-01

Adsorption of H2O and its effect on CO oxidation over spinel Co3O4 (110) surface were studied by density functional theory calculations. H2O is adsorbed favorably at the octahedral cobalt (Cooct) site through O atom on the surface. Hydrogen bonding interaction between 1s orbitals of H atoms in H2O and the 2p orbitals of surface active oxygen sites plays a key role for H2O adsorption. The inhibition effect of H2O adsorption on the CO oxidation over the surfaces is attributed to the competition between H2O and CO molecules for the surface twofold coordinated oxygen site.

Different CO2 absorbents-modified SBA-15 sorbent for highly selective CO2 capture

NASA Astrophysics Data System (ADS)

Liu, Xiuwu; Zhai, Xinru; Liu, Dongyang; Sun, Yan

2017-05-01

Different CO2 absorbents-modified SBA-15 materials are used as CO2 sorbent to improve the selectivity of CH4/CO2 separation. The SBA-15 sorbents modified by physical CO2 absorbents are very limited to increasing CO2 adsorption and present poor selectivity. However, the SBA-15 sorbents modified by chemical CO2 absorbents increase CO2 adsorption capacity obviously. The separation coefficients of CO2/CH4 increase in this case. The adsorption and regeneration properties of the SBA-15 sorbents modified by TEA, MDEA and DIPA have been compared. The SBA-15 modified by triethanolamine (TEA) presents better CO2/CH4 separation performance than the materials modified by other CO2 absorbents.

A Genetically Defined Circuit for Arousal from Sleep during Hypercapnia.

PubMed

Kaur, Satvinder; Wang, Joshua L; Ferrari, Loris; Thankachan, Stephen; Kroeger, Daniel; Venner, Anne; Lazarus, Michael; Wellman, Andrew; Arrigoni, Elda; Fuller, Patrick M; Saper, Clifford B

2017-12-06

The precise neural circuitry that mediates arousal during sleep apnea is not known. We previously found that glutamatergic neurons in the external lateral parabrachial nucleus (PBel) play a critical role in arousal to elevated CO2 or hypoxia. Because many of the PBel neurons that respond to CO2 express calcitonin gene-related peptide (CGRP), we hypothesized that CGRP may provide a molecular identifier of the CO2 arousal circuit. Here, we report that selective chemogenetic and optogenetic activation of PBel CGRP neurons caused wakefulness, whereas optogenetic inhibition of PBel CGRP neurons prevented arousal to CO2, but not to an acoustic tone or shaking. Optogenetic inhibition of PBel CGRP terminals identified a network of forebrain sites under the control of a PBel CGRP switch that is necessary to arouse animals from hypercapnia. Our findings define a novel cellular target for interventions that may prevent sleep fragmentation and the attendant cardiovascular and cognitive consequences seen in obstructive sleep apnea. VIDEO ABSTRACT. Copyright © 2017 Elsevier Inc. All rights reserved.

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

DOE PAGES

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; ...

2017-04-25

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Infrared spectra of RuTPP, RuCOTPP, and Ru(CO)2TPP isolated in solid argon.

PubMed

Krim, Lahouari; Sorgues, Sébastien; Soep, Benoit; Shafizadeh, Niloufar

2005-09-22

Infrared spectra of unstable species such as CO-free ruthenium tetraphenylporphyrin RuTPP and RuCOTPP (species with vacant coordination sites) isolated in solid argon at 8 K have been recorded. Selective deposition conditions allow the isolation of either RuTPP and RuCOTPP or RuCOTPP and Ru(CO)2TPP. This depends on the preparation conditions of the sample. A specific Ru-CO bending mode has been characterized at 590.1 cm(-1) for Ru(CO)2TPP. The behavior of each vibrational mode of RuTPP, RuCOTPP, and Ru(CO)2TPP has been analyzed. Modes such as gamma8 at 721.3 cm(-1) (out-of-plane stretching mode gamma(Cbeta-H)sym) and nu41 at 1342.8 cm(-1) (nuCalpha-N coupled with deltaCalpha-Cm) reflect the charge transfer in the porphyrin. Indeed, the addition of one or two CO ligands to RuTPP reduces the charge transfer between the metal center and the porphyrin, which appears as an increase in the frequency of the nu41 mode and in a decrease in that of the gamma8 mode.

Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO) 4 –-incorporated Cr-MIL-101

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Hoyoung D.; Dinca, Mircea; Roman-Leshkov, Yuriy

Here, despite the commercial desirability of epoxide carbonylation to β-lactones, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO) 4 –-incorporated Cr-MIL-101 (Co(CO) 4cCr-MIL-101, Cr-MIL-101 = Cr 3O(BDC) 3F, H2BDC = 1,4-benzenedicarboxylic acid) heterogeneous catalyst for the ring-expansion carbonylation of epoxides, whose activity, selectivity, and substrate scope are on par with those of the reported homogeneous catalysts. We ascribe the observed performance to the unique cooperativity between the postsynthetically introduced Co(CO) 4 – and the site-isolated Lewis acidic Cr(III) centers in the metal–organic framework (MOF). Themore » heterogeneous nature of Co(CO) 4cCr-MIL-101 allows the first demonstration of gas-phase continuous-flow production of β-lactones from epoxides, attesting to the potential applicability of the heterogeneous epoxide carbonylation strategy.« less

Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO) 4 –-incorporated Cr-MIL-101

DOE PAGES

Park, Hoyoung D.; Dinca, Mircea; Roman-Leshkov, Yuriy

2017-03-21

Here, despite the commercial desirability of epoxide carbonylation to β-lactones, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO) 4 –-incorporated Cr-MIL-101 (Co(CO) 4cCr-MIL-101, Cr-MIL-101 = Cr 3O(BDC) 3F, H2BDC = 1,4-benzenedicarboxylic acid) heterogeneous catalyst for the ring-expansion carbonylation of epoxides, whose activity, selectivity, and substrate scope are on par with those of the reported homogeneous catalysts. We ascribe the observed performance to the unique cooperativity between the postsynthetically introduced Co(CO) 4 – and the site-isolated Lewis acidic Cr(III) centers in the metal–organic framework (MOF). Themore » heterogeneous nature of Co(CO) 4cCr-MIL-101 allows the first demonstration of gas-phase continuous-flow production of β-lactones from epoxides, attesting to the potential applicability of the heterogeneous epoxide carbonylation strategy.« less

Los Angeles megacity: a high-resolution land–atmosphere modelling system for urban CO 2 emissions

DOE PAGES

Feng, Sha; Lauvaux, Thomas; Newman, Sally; ...

2016-07-22

Megacities are major sources of anthropogenic fossil fuel CO 2 (FFCO 2) emissions. The spatial extents of these large urban systems cover areas of 10 000 km 2 or more with complex topography and changing landscapes. We present a high-resolution land–atmosphere modelling system for urban CO 2 emissions over the Los Angeles (LA) megacity area. The Weather Research and Forecasting (WRF)-Chem model was coupled to a very high-resolution FFCO 2 emission product, Hestia-LA, to simulate atmospheric CO 2 concentrations across the LA megacity at spatial resolutions as fine as ~1 km. We evaluated multiple WRF configurations, selecting one that minimizedmore » errors in wind speed, wind direction, and boundary layer height as evaluated by its performance against meteorological data collected during the CalNex-LA campaign (May–June 2010). Our results show no significant difference between moderate-resolution (4 km) and high-resolution (1.3 km) simulations when evaluated against surface meteorological data, but the high-resolution configurations better resolved planetary boundary layer heights and vertical gradients in the horizontal mean winds. We coupled our WRF configuration with the Vulcan 2.2 (10 km resolution) and Hestia-LA (1.3 km resolution) fossil fuel CO 2 emission products to evaluate the impact of the spatial resolution of the CO 2 emission products and the meteorological transport model on the representation of spatiotemporal variability in simulated atmospheric CO 2 concentrations. We find that high spatial resolution in the fossil fuel CO 2 emissions is more important than in the atmospheric model to capture CO 2 concentration variability across the LA megacity. Finally, we present a novel approach that employs simultaneous correlations of the simulated atmospheric CO 2 fields to qualitatively evaluate the greenhouse gas measurement network over the LA megacity. Spatial correlations in the atmospheric CO 2 fields reflect the coverage of individual measurement sites when a statistically significant number of sites observe emissions from a specific source or location. We conclude that elevated atmospheric CO 2 concentrations over the LA megacity are composed of multiple fine-scale plumes rather than a single homogenous urban dome. Furthermore, we conclude that FFCO 2 emissions monitoring in the LA megacity requires FFCO 2 emissions modelling with ~1 km resolution because coarser-resolution emissions modelling tends to overestimate the observational constraints on the emissions estimates.« less

Los Angeles megacity: a high-resolution land–atmosphere modelling system for urban CO 2 emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Sha; Lauvaux, Thomas; Newman, Sally

Megacities are major sources of anthropogenic fossil fuel CO 2 (FFCO 2) emissions. The spatial extents of these large urban systems cover areas of 10 000 km 2 or more with complex topography and changing landscapes. We present a high-resolution land–atmosphere modelling system for urban CO 2 emissions over the Los Angeles (LA) megacity area. The Weather Research and Forecasting (WRF)-Chem model was coupled to a very high-resolution FFCO 2 emission product, Hestia-LA, to simulate atmospheric CO 2 concentrations across the LA megacity at spatial resolutions as fine as ~1 km. We evaluated multiple WRF configurations, selecting one that minimizedmore » errors in wind speed, wind direction, and boundary layer height as evaluated by its performance against meteorological data collected during the CalNex-LA campaign (May–June 2010). Our results show no significant difference between moderate-resolution (4 km) and high-resolution (1.3 km) simulations when evaluated against surface meteorological data, but the high-resolution configurations better resolved planetary boundary layer heights and vertical gradients in the horizontal mean winds. We coupled our WRF configuration with the Vulcan 2.2 (10 km resolution) and Hestia-LA (1.3 km resolution) fossil fuel CO 2 emission products to evaluate the impact of the spatial resolution of the CO 2 emission products and the meteorological transport model on the representation of spatiotemporal variability in simulated atmospheric CO 2 concentrations. We find that high spatial resolution in the fossil fuel CO 2 emissions is more important than in the atmospheric model to capture CO 2 concentration variability across the LA megacity. Finally, we present a novel approach that employs simultaneous correlations of the simulated atmospheric CO 2 fields to qualitatively evaluate the greenhouse gas measurement network over the LA megacity. Spatial correlations in the atmospheric CO 2 fields reflect the coverage of individual measurement sites when a statistically significant number of sites observe emissions from a specific source or location. We conclude that elevated atmospheric CO 2 concentrations over the LA megacity are composed of multiple fine-scale plumes rather than a single homogenous urban dome. Furthermore, we conclude that FFCO 2 emissions monitoring in the LA megacity requires FFCO 2 emissions modelling with ~1 km resolution because coarser-resolution emissions modelling tends to overestimate the observational constraints on the emissions estimates.« less

Atmospheric CO and hydrogen uptake and CO oxidizer phylogeny for miyake-jima, Japan volcanic deposits.

PubMed

King, Gary M; Weber, Carolyn F; Nanba, Kenji; Sato, Yoshinori; Ohta, Hiroyuki

2008-01-01

We have assayed rates of atmospheric CO and hydrogen uptake, maximum potential CO uptake and the major phylogenetic composition of CO-oxidizing bacterial communities for a variety of volcanic deposits on Miyake-jima, Japan. These deposits represented different ages and stages of plant succession, ranging from unvegetated scoria deposited in 1983 to forest soils on deposits >800 yr old. Atmospheric CO and hydrogen uptake rates varied from -2.0±1.8-6.3±0.1 mg CO m(-2) d(-1) and 0.0±0.4-2.0±0.2 mg H(2) m(-2) d(-1), respectively, and were similar to or greater than values reported for sites on Kilauea volcano, Hawaii, USA. At one of the forested sites, CO was emitted to the atmosphere, while two vegetated sites did not consume atmospheric hydrogen, an unusual observation. Although maximum potential CO uptake rates were also comparable to values for Kilauea, the relationship between these rates and organic carbon contents of scoria or soil indicated that CO oxidizers were relatively more abundant in Miyake-jima deposits. Phylogenetic analyses based on the large sub-unit gene for carbon monoxide dehydrogenase (coxL) indicated that many novel lineages were present on Miyake-jima, that CO-oxidizing Proteobacteria were prevalent in vegetated sites and that community structure appeared to vary more than composition among sites.

Geochemical Influence on Microbial Communities at CO2-Leakage Analog Sites.

PubMed

Ham, Baknoon; Choi, Byoung-Young; Chae, Gi-Tak; Kirk, Matthew F; Kwon, Man Jae

2017-01-01

Microorganisms influence the chemical and physical properties of subsurface environments and thus represent an important control on the fate and environmental impact of CO 2 that leaks into aquifers from deep storage reservoirs. How leakage will influence microbial populations over long time scales is largely unknown. This study uses natural analog sites to investigate the long-term impact of CO 2 leakage from underground storage sites on subsurface biogeochemistry. We considered two sites with elevated CO 2 levels (sample groups I and II) and one control site with low CO 2 content (group III). Samples from sites with elevated CO 2 had pH ranging from 6.2 to 4.5 and samples from the low-CO 2 control group had pH ranging from 7.3 to 6.2. Solute concentrations were relatively low for samples from the control group and group I but high for samples from group II, reflecting varying degrees of water-rock interaction. Microbial communities were analyzed through clone library and MiSeq sequencing. Each 16S rRNA analysis identified various bacteria, methane-producing archaea, and ammonia-oxidizing archaea. Both bacterial and archaeal diversities were low in groundwater with high CO 2 content and community compositions between the groups were also clearly different. In group II samples, sequences classified in groups capable of methanogenesis, metal reduction, and nitrate reduction had higher relative abundance in samples with relative high methane, iron, and manganese concentrations and low nitrate levels. Sequences close to Comamonadaceae were abundant in group I, while the taxa related to methanogens, Nitrospirae , and Anaerolineaceae were predominant in group II. Our findings provide insight into subsurface biogeochemical reactions that influence the carbon budget of the system including carbon fixation, carbon trapping, and CO 2 conversion to methane. The results also suggest that monitoring groundwater microbial community can be a potential tool for tracking CO 2 leakage from geologic storage sites.

Geochemical Influence on Microbial Communities at CO2-Leakage Analog Sites

PubMed Central

Ham, Baknoon; Choi, Byoung-Young; Chae, Gi-Tak; Kirk, Matthew F.; Kwon, Man Jae

2017-01-01

Microorganisms influence the chemical and physical properties of subsurface environments and thus represent an important control on the fate and environmental impact of CO2 that leaks into aquifers from deep storage reservoirs. How leakage will influence microbial populations over long time scales is largely unknown. This study uses natural analog sites to investigate the long-term impact of CO2 leakage from underground storage sites on subsurface biogeochemistry. We considered two sites with elevated CO2 levels (sample groups I and II) and one control site with low CO2 content (group III). Samples from sites with elevated CO2 had pH ranging from 6.2 to 4.5 and samples from the low-CO2 control group had pH ranging from 7.3 to 6.2. Solute concentrations were relatively low for samples from the control group and group I but high for samples from group II, reflecting varying degrees of water-rock interaction. Microbial communities were analyzed through clone library and MiSeq sequencing. Each 16S rRNA analysis identified various bacteria, methane-producing archaea, and ammonia-oxidizing archaea. Both bacterial and archaeal diversities were low in groundwater with high CO2 content and community compositions between the groups were also clearly different. In group II samples, sequences classified in groups capable of methanogenesis, metal reduction, and nitrate reduction had higher relative abundance in samples with relative high methane, iron, and manganese concentrations and low nitrate levels. Sequences close to Comamonadaceae were abundant in group I, while the taxa related to methanogens, Nitrospirae, and Anaerolineaceae were predominant in group II. Our findings provide insight into subsurface biogeochemical reactions that influence the carbon budget of the system including carbon fixation, carbon trapping, and CO2 conversion to methane. The results also suggest that monitoring groundwater microbial community can be a potential tool for tracking CO2 leakage from geologic storage sites. PMID:29170659

One-pot synthesis of CdS nanocrystals hybridized with single-layer transition-metal dichalcogenide nanosheets for efficient photocatalytic hydrogen evolution.

PubMed

Chen, Junze; Wu, Xue-Jun; Yin, Lisha; Li, Bing; Hong, Xun; Fan, Zhanxi; Chen, Bo; Xue, Can; Zhang, Hua

2015-01-19

Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10 nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16 h), and 70% of catalytic activity still remained. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular simulation of CO2/CH4 adsorption in brown coal: Effect of oxygen-, nitrogen-, and sulfur-containing functional groups

NASA Astrophysics Data System (ADS)

Dang, Yong; Zhao, Lianming; Lu, Xiaoqing; Xu, Jing; Sang, Pengpeng; Guo, Sheng; Zhu, Houyu; Guo, Wenyue

2017-11-01

The CO2/CH4 adsorption behaviors in brown coal at the temperatures of 298, 313, and 373 K and in the pressure range of 0.005-10 MPa were investigated by molecular dynamics (MD), density functional theory (DFT), and grand canonical Monte Carlo (GCMC) simulations. The absolute adsorption isotherms of single-component CH4 and CO2 exhibit type-I Langmuir adsorption behavior showing a negative influence of temperature. For the binary CO2/CH4 mixture, brown coal shows super high selectivity of CO2 over CH4 at pressures below 0.2 MPa, which then decreases quickly and finally tends to be constant when the pressure increases. The high competitive adsorption of CO2 originates from the effects of (i) the large electrostatic contributions, (ii) the conducive micropore environment with pore sizes below 0.56 nm, and (iii) the stronger adsorption of CO2 with respect to CH4. These effects are strengthened by the high-density oxygen-containing, pyridine, and thiophene functional groups contained in brown coal, which provide abundant and strong adsorption sites for CO2, but show weaker affinity to CH4. Furthermore, the influence of various nitrogen- and sulfur-containing functional groups on the CO2 adsorption capacity was also investigated. The results indicate that the basicity of the oxygen- and nitrogen-containing groups has a large influence on the CO2 adsorption, while for the sulfur functional groups the determining factor is the polarity.

Verification of geomechanical integrity and prediction of long-term mineral trapping for the Ketzin CO2 storage pilot site

NASA Astrophysics Data System (ADS)

Kempka, Thomas; De Lucia, Marco; Kühn, Michael

2014-05-01

Static and dynamic numerical modelling generally accompany the entire CO2 storage site life cycle. Thereto, it is required to match the employed models with field observations on a regular basis in order to predict future site behaviour. We investigated the coupled processes at the Ketzin CO2 storage pilot site [1] using a model coupling concept focusing on the temporal relevance of processes involved (hydraulic, chemical and mechanical) at given time-scales (site operation, abandonment and long-term stabilization). For that purpose, long-term dynamic multi-phase flow simulations [2], [3] established the basis for all simulations discussed in the following. Hereby, pressure changes resulting in geomechanical effects are largest during site operation, whereas geochemical reactions are governed by slow kinetics resulting in a long-term stabilization. To account for mechanical integrity, which may be mainly affected during site operation, we incorporated a regional-scale coupled hydro-mechanical model. Our simulation results show maximum ground surface displacements of about 4 mm, whereas shear and tensile failure are not observed. Consequently, the CO2 storage operation at the Ketzin pilot site does not compromise reservoir, caprock and fault integrity. Chemical processes responsible for mineral trapping are expected to mainly occur during long-term stabilization at the Ketzin pilot site [4]. Hence, our previous assessment [3] was extended by integrating two long-term mineral trapping scenarios. Thereby, mineral trapping contributes to the trapping mechanisms with 11.7 % after 16,000 years of simulation in our conservative and with 30.9 % in our maximum reactivity scenarios. Dynamic flow simulations indicate that only 0.2 % of the CO2 injected (about 67,270 t CO2 in total) is in gaseous state, but structurally trapped after 16,000 years. Depending on the studied long-term scenario, CO2 dissolution is the dominating trapping mechanism with 68.9 % and 88.1 %, respectively. We verified the mechanical integrity of the storage system during site operation and predicted the trapping mechanisms for the Ketzin pilot site based on a time-dependent integration of relevant processes for a time period of 16,000 years. Supported by our coupled modelling results, we conclude that CO2 storage at the Ketzin site is safe and reliable on the pilot scale. References [1] Martens, S., Kempka, T., Liebscher, A., Lüth, S., Möller, F., Myrttinen, A., Norden, B., Schmidt-Hattenberger, C., Zimmer, M., Kühn, M. Europe's longest-operating on-shore CO2 storage site at Ketzin, Germany: a progress report after three years of injection. Environmental Earth Sciences 2012 67(2): 323-334. [2] Kempka, T., Kühn, M. Numerical simulations of CO2 arrival times and reservoir pressure coincide with observations from the Ketzin pilot site, Germany. Environmental Earth Sciences 2013 70(8): 3675-3685. [3] Kempka, T., Klein, E., De Lucia, M., Tillner, E., Kühn, M. Assessment of Long-term CO2 Trapping Mechanisms at the Ketzin Pilot Site (Germany) by Coupled Numerical Modelling. Energy Procedia 2013 37: 5419-5426. [4] Klein, E., De Lucia, M., Kempka, T., Kühn, M. Evaluation of long-term mineral trapping at the Ketzin pilot site for CO2 storage: An integrative approach using geochemical modelling and reservoir simulation. International Journal of Greenhouse Gas Control 2013 19: 720-730.

Comparisons of a Quantum Annealing and Classical Computer Neural Net Approach for Inferring Global Annual CO2 Fluxes over Land

NASA Astrophysics Data System (ADS)

Halem, M.; Radov, A.; Singh, D.

2017-12-01

Investigations of mid to high latitude atmospheric CO2 show growing amplitudes in seasonal variations over the past several decades. Recent high-resolution satellite measurements of CO2 concentration are now available for three years from the Orbiting Carbon Observatory-2. The Atmospheric Radiation Measurement (ARM) program of DOE has been making long-term CO2-flux measurements (in addition to CO2 concentration and an array of other meteorological quantities) at several towers and mobile sites located around the globe at half-hour frequencies. Recent papers have shown CO2 fluxes inferred by assimilating CO2 observations into ecosystem models are largely inconsistent with station observations. An investigation of how the biosphere has reacted to changes in atmospheric CO2 is essential to our understanding of potential climate-vegetation feedbacks. Thus, new approaches for calculating CO2-flux for assimilation into land surface models are necessary for improving the prediction of annual carbon uptake. In this study, we calculate and compare the predicted CO2 fluxes results employing a Feed Forward Backward Propagation Neural Network model on two architectures, (i) an IBM Minsky Computer node and (ii) a hybrid version of the ARC D-Wave quantum annealing computer. We compare the neural net results of predictions of CO2 flux from ARM station data for three different DOE ecosystem sites; an arid plains near Oklahoma City, a northern arctic site at Barrows AL, and a tropical rainforest site in the Amazon. Training times and predictive results for the calculating annual CO2 flux for the two architectures for each of the three sites are presented. Comparative results of predictions as measured by RMSE and MAE are discussed. Plots and correlations of observed vs predicted CO2 flux are also presented for all three sites. We show the estimated training times for quantum and classical calculations when extended to calculating global annual Carbon Uptake over land. We also examine the efficiency, dependability and resilience of the quantum neural net approach relative to classical computer systems in predicting annual CO2 flux globally.

Energy Use and Carbon Dioxide Emissions from Cropland Production in the United States, 1990-2004

DOE Office of Scientific and Technical Information (OSTI.GOV)

West, Tristram O.; Brandt, Craig C; Marland, Gregg

2009-01-01

Changes in cropland production and management influence energy consumption and emissions of CO2 from fossil-fuel combustion. A method was developed to calculate on-site and off-site energy and CO2 emissions for cropping practices in the US at the county scale. Energy consumption and emissions occur on-site from the operation of farm machinery and occur off-site from the manufacture and transport of cropland production inputs, such as fertilizers, pesticides, and agricultural lime. Estimates of fossil-fuel consumption and associated CO2 emissions for cropping practices enable (a) the monitoring of energy and emissions with changes in land management, and (b) the calculation and balancingmore » of regional and national carbon budgets. Results indicate on-site energy use and total energy use (i.e., the sum of on-site and off-site) on US croplands in 2004 ranged from 1.6-7.9 GJ ha-1 yr-1 and from 5.5-20.5 GJ ha-1 yr-1, respectively. On-site and total CO2 emissions in 2004 ranged from 23-176 kg C ha-1 yr-1 and from 91-365 kg C ha-1 yr-1, respectively. During the period of this analysis (1990-2004), national total energy consumption for crop production ranged from 1204-1297 PJ yr-1 (Petajoule = 1 1015 Joule) with associated total fossil CO2 emissions ranging from 22.0-23.2 Tg C yr-1 (Teragram = 1 1012 gram). The annual proportion of on-site CO2 to total CO2 emissions changed depending on the diversity of crops planted. Adoption of reduced tillage practices in the US from 1990 to 2004 resulted in a net emissions reduction of 2.4 Tg C.« less

The stable microbiome of inter and sub-tidal anemone species under increasing pCO2

PubMed Central

Muller, Erinn M.; Fine, Maoz; Ritchie, Kim B.

2016-01-01

Increasing levels of pCO2 within the oceans will select for resistant organisms such as anemones, which may thrive under ocean acidification conditions. However, increasing pCO2 may alter the bacterial community of marine organisms, significantly affecting the health status of the host. A pH gradient associated with a natural volcanic vent system within Levante Bay, Vulcano Island, Italy, was used to test the effects of ocean acidification on the bacterial community of two anemone species in situ, Anemonia viridis and Actinia equina using 16 S rDNA pyrosequencing. Results showed the bacterial community of the two anemone species differed significantly from each other primarily because of differences in the Gammaproteobacteria and Epsilonproteobacteria abundances. The bacterial communities did not differ within species among sites with decreasing pH except for A. viridis at the vent site (pH = 6.05). In addition to low pH, the vent site contains trace metals and sulfide that may have influenced the bacteria community of A. viridis. The stability of the bacterial community from pH 8.1 to pH 7.4, coupled with previous experiments showing the lack of, or beneficial changes within anemones living under low pH conditions indicates that A. viridis and A. equina will be winners under future ocean acidification scenarios. PMID:27876762

The stable microbiome of inter and sub-tidal anemone species under increasing pCO2

NASA Astrophysics Data System (ADS)

Muller, Erinn M.; Fine, Maoz; Ritchie, Kim B.

2016-11-01

Increasing levels of pCO2 within the oceans will select for resistant organisms such as anemones, which may thrive under ocean acidification conditions. However, increasing pCO2 may alter the bacterial community of marine organisms, significantly affecting the health status of the host. A pH gradient associated with a natural volcanic vent system within Levante Bay, Vulcano Island, Italy, was used to test the effects of ocean acidification on the bacterial community of two anemone species in situ, Anemonia viridis and Actinia equina using 16 S rDNA pyrosequencing. Results showed the bacterial community of the two anemone species differed significantly from each other primarily because of differences in the Gammaproteobacteria and Epsilonproteobacteria abundances. The bacterial communities did not differ within species among sites with decreasing pH except for A. viridis at the vent site (pH = 6.05). In addition to low pH, the vent site contains trace metals and sulfide that may have influenced the bacteria community of A. viridis. The stability of the bacterial community from pH 8.1 to pH 7.4, coupled with previous experiments showing the lack of, or beneficial changes within anemones living under low pH conditions indicates that A. viridis and A. equina will be winners under future ocean acidification scenarios.

Stability-activity tradeoffs constrain the adaptive evolution of RubisCO.

PubMed

Studer, Romain A; Christin, Pascal-Antoine; Williams, Mark A; Orengo, Christine A

2014-02-11

A well-known case of evolutionary adaptation is that of ribulose-1,5-bisphosphate carboxylase (RubisCO), the enzyme responsible for fixation of CO2 during photosynthesis. Although the majority of plants use the ancestral C3 photosynthetic pathway, many flowering plants have evolved a derived pathway named C4 photosynthesis. The latter concentrates CO2, and C4 RubisCOs consequently have lower specificity for, and faster turnover of, CO2. The C4 forms result from convergent evolution in multiple clades, with substitutions at a small number of sites under positive selection. To understand the physical constraints on these evolutionary changes, we reconstructed in silico ancestral sequences and 3D structures of RubisCO from a large group of related C3 and C4 species. We were able to precisely track their past evolutionary trajectories, identify mutations on each branch of the phylogeny, and evaluate their stability effect. We show that RubisCO evolution has been constrained by stability-activity tradeoffs similar in character to those previously identified in laboratory-based experiments. The C4 properties require a subset of several ancestral destabilizing mutations, which from their location in the structure are inferred to mainly be involved in enhancing conformational flexibility of the open-closed transition in the catalytic cycle. These mutations are near, but not in, the active site or at intersubunit interfaces. The C3 to C4 transition is preceded by a sustained period in which stability of the enzyme is increased, creating the capacity to accept the functionally necessary destabilizing mutations, and is immediately followed by compensatory mutations that restore global stability.

Drug delivery from hydrophobic-modified mesoporous silicas: Control via modification level and site-selective modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang Qunli, E-mail: tangqunli@hnu.c; State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001; Chen Yuxi

2010-01-15

Dimethylsilyl (DMS) modified mesoporous silicas were successfully prepared via co-condensation and post-grafting modification methods. The post-grafting modification was carried out by the reaction of the as-synthesized MCM-41 material (before CTAB removal) with diethoxydimethylsinale (DEDMS). N{sub 2} adsorption-desorption and {sup 29}Si MAS NMR characterization demonstrated that different amount of DMS groups were successfully incorporated into the co-condensation modified samples, and the functional DMS groups were placed selectively on the pore openings and external pore surfaces in the post-grafting modified samples. Subsequently, the controlled drug delivery properties from the resulting DMS-modified mesoporous silicas were investigated in detail. The drug adsorption experiments showedmore » that the adsorption capacities were mainly depended on the content of silanol group (CSG) in the corresponding carriers. The in vitro tests exhibited that the incorporation of DMS groups greatly retarded the ibuprofen release rate. Moreover, the ibuprofen release profiles could be well modulated by varying DMS modification levels and site-selective distribution of functional groups in mesoporous carriers. - The distribution of DMS groups on the pore surfaces of the mesostructures strongly affects the drug release rate. The P-M41-1 and the P-M41-2 possess the close DMS modification levels as the C-M41-10, but the ibuprofen release rates from the P-M41-1 and P-M41-2 are much slower than that from the C-M41-10.« less

Evaluation of stormwater harvesting sites using multi criteria decision methodology

NASA Astrophysics Data System (ADS)

Inamdar, P. M.; Sharma, A. K.; Cook, Stephen; Perera, B. J. C.

2018-07-01

Selection of suitable urban stormwater harvesting sites and associated project planning are often complex due to spatial, temporal, economic, environmental and social factors, and related various other variables. This paper is aimed at developing a comprehensive methodology framework for evaluating of stormwater harvesting sites in urban areas using Multi Criteria Decision Analysis (MCDA). At the first phase, framework selects potential stormwater harvesting (SWH) sites using spatial characteristics in a GIS environment. In second phase, MCDA methodology is used for evaluating and ranking of SWH sites in multi-objective and multi-stakeholder environment. The paper briefly describes first phase of framework and focuses chiefly on the second phase of framework. The application of the methodology is also demonstrated over a case study comprising of the local government area, City of Melbourne (CoM), Australia for the benefit of wider water professionals engaged in this area. Nine performance measures (PMs) were identified to characterise the objectives and system performance related to the eight alternative SWH sites for the demonstration of the application of developed methodology. To reflect the stakeholder interests in the current study, four stakeholder participant groups were identified, namely, water authorities (WA), academics (AC), consultants (CS), and councils (CL). The decision analysis methodology broadly consisted of deriving PROMETHEE II rankings of eight alternative SWH sites in the CoM case study, under two distinct group decision making scenarios. The major innovation of this work is the development and application of comprehensive methodology framework that assists in the selection of potential sites for SWH, and facilitates the ranking in multi-objective and multi-stakeholder environment. It is expected that the proposed methodology will assist the water professionals and managers with better knowledge that will reduce the subjectivity in the selection and evaluation of SWH sites.

Confirmation of high-throughput screening data and novel mechanistic insights into VDR-xenobiotic interactions by orthogonal assays.

PubMed

Mahapatra, Debabrata; Franzosa, Jill A; Roell, Kyle; Kuenemann, Melaine Agnes; Houck, Keith A; Reif, David M; Fourches, Denis; Kullman, Seth W

2018-06-11

High throughput screening (HTS) programs have demonstrated that the Vitamin D receptor (VDR) is activated and/or antagonized by a wide range of structurally diverse chemicals. In this study, we examined the Tox21 qHTS data set generated against VDR for reproducibility and concordance and elucidated functional insights into VDR-xenobiotic interactions. Twenty-one potential VDR agonists and 19 VDR antagonists were identified from a subset of >400 compounds with putative VDR activity and examined for VDR functionality utilizing select orthogonal assays. Transient transactivation assay (TT) using a human VDR plasmid and Cyp24 luciferase reporter construct revealed 20/21 active VDR agonists and 18/19 active VDR antagonists. Mammalian-2-hybrid assay (M2H) was then used to evaluate VDR interactions with co-activators and co-regulators. With the exception of a select few compounds, VDR agonists exhibited significant recruitment of co-regulators and co-activators whereas antagonists exhibited considerable attenuation of recruitment by VDR. A unique set of compounds exhibiting synergistic activity in antagonist mode and no activity in agonist mode was identified. Cheminformatics modeling of VDR-ligand interactions were conducted and revealed selective ligand VDR interaction. Overall, data emphasizes the molecular complexity of ligand-mediated interactions with VDR and suggest that VDR transactivation may be a target site of action for diverse xenobiotics.

Implications for carbon processing beneath the Greenland Ice Sheet from dissolved CO2 and CH4 concentrations of subglacial discharge

NASA Astrophysics Data System (ADS)

Pain, A.; Martin, J.; Martin, E. E.

2017-12-01

Subglacial carbon processes are of increasing interest as warming induces ice melting and increases fluxes of glacial meltwater into proglacial rivers and the coastal ocean. Meltwater may serve as an atmospheric source or sink of carbon dioxide (CO2) or methane (CH4), depending on the magnitudes of subglacial organic carbon (OC) remineralization, which produces CO2 and CH4, and mineral weathering reactions, which consume CO2 but not CH4. We report wide variability in dissolved CO2 and CH4 concentrations at the beginning of the melt season (May-June 2017) between three sites draining land-terminating glaciers of the Greenland Ice Sheet. Two sites, located along the Watson River in western Greenland, drain the Isunnguata and Russell Glaciers and contained 1060 and 400 ppm CO2, respectively. In-situ CO2 flux measurements indicated that the Isunnguata was a source of atmospheric CO2, while the Russell was a sink. Both sites had elevated CH4 concentrations, at 325 and 25 ppm CH4, respectively, suggesting active anaerobic OC remineralization beneath the ice sheet. Dissolved CO2 and CH4 reached atmospheric equilibrium within 2.6 and 8.6 km downstream of Isunnguata and Russell discharge sites, respectively. These changes reflect rapid gas exchange with the atmosphere and/or CO2 consumption via instream mineral weathering. The third site, draining the Kiagtut Sermiat in southern Greenland, had about half atmospheric CO2 concentrations (250 ppm), but approximately atmospheric CH4 concentrations (2.1 ppm). Downstream CO2 flux measurements indicated ingassing of CO2 over the entire 10-km length of the proglacial river. CO2 undersaturation may be due to more readily weathered lithologies underlying the Kiagtut Sermiat compared to Watson River sites, but low CH4 concentrations also suggest limited contributions of CO2 and CH4 from OC remineralization. These results suggest that carbon processing beneath the Greenland Ice Sheet may be more variable than previously recognized. Variations control whether discharge is a source or sink of atmospheric CO2 or CH4, but gas concentrations could be further modified by instream reactions. Increased meltwater fluxes should enhance the importance of greenhouse gas fluxes from subglacial discharge, and heighten the need to constrain variability in subglacial carbon processing.

Toward improving CO2 dissociation and conversion to methanol via CO-hydrogenation on Cu(100) surface by introducing embedded Co nanoclusters as promoters: A DFT study

NASA Astrophysics Data System (ADS)

Qiu, Mei; Tao, Huilin; Li, Yali; Li, Yi; Ding, Kaining; Huang, Xin; Chen, Wenkai; Zhang, Yongfan

2018-01-01

The dissociation and hydrogenation of CO2 on Cu(100) surfaces that are modified by introducing Co nanoclusters with different size into the top layer have been investigated using density functional theory method. Our results show that on all surfaces the Co atoms are the sites for the adsorption of CO2, and in the early stage of introducing Co dopant, the chemisorption behavior of CO2 is sensitive to the amount of Co atom. According to the predicted pathways for the dissociation of CO2 to CO, it is interesting that the energy barrier decreases first and then increases as more Co atoms are dispersed on the surface, forming a ;V; shape. The minimum energy barrier of CO2 decomposition is predicted on the Cu(100) surface that contains four Co atoms aggregated together on the top layer, namely Co4/Cu(100) bimetallic surface. The most favorable reaction pathway for the hydrogenation of CO to methanol on such surface is further determined, which follows the sequence of CO* → HCO* → H2CO* → H3CO* → H3COH*, and the rate-limiting step is the hydrogenation of H3CO species with an activation barrier of 106.4 kJ/mol. It is noted that with respect to the pure Cu(100), since more stronger Cosbnd O adsorption bonds are formed on the Co-modified surface, the stability of formaldehyde intermediate is significantly enhanced. Correspondingly, the introducing of Co4 cluster tends to improve the productivity and selectivity towards methanol synthesis on Cu(100) surface.

Towards a physiological basis for intensive culture of American sycamore, Platanus occidentalis L

DOE Office of Scientific and Technical Information (OSTI.GOV)

McVay, M.E.

1984-01-01

The light environment of forest canopies is complex leading to differentiation in morphological development and alteration of physiological processes that are important for the proper combination of genotype and site factors to maximize final yield. To select leaves and plants of a uniform age plastochron and leaf plastochron indices were developed for American sycamore Platanus occidentalis L. The application of these indices was useful in selecting a population of plants of uniform age and, morphological development, and useful in selecting leaves of uniform age within the zone of leaf development. Labeling studies in which leaves of specific ages were fedmore » /sup 14/CO/sub 2/ indicated that leaves of this species undergo transitions in degree and direction of export. Acropetal export of photosynthates conforms to a phyllotactic sequence, suggesting a relationship between arrangement of vascular bundles and phyllotaxy. Examination of the /sup 14/CO/sub 2/ labeling patterns in source leaves (LPI 2.0) showed rapid incorporation of label into amino acid, sugar, and organic acid chemical pools that can be used to in situ synthesis of proteins, lipids, and other structural components. However as the irradiance regime under which the plants were grown decreased, leaves partitioned more fixed /sup 14/CO/sub 2/ into starch than into the water soluble fraction from which metabolic and structural components as well as a transport species could be synthesized.« less

Atomic layer deposition overcoating: tuning catalyst selectivity for biomass conversion.

PubMed

Zhang, Hongbo; Gu, Xiang-Kui; Canlas, Christian; Kropf, A Jeremy; Aich, Payoli; Greeley, Jeffrey P; Elam, Jeffrey W; Meyers, Randall J; Dumesic, James A; Stair, Peter C; Marshall, Christopher L

2014-11-03

The terraces, edges, and facets of nanoparticles are all active sites for heterogeneous catalysis. These different active sites may cause the formation of various products during the catalytic reaction. Here we report that the step sites of Pd nanoparticles (NPs) can be covered precisely by the atomic layer deposition (ALD) method, whereas the terrace sites remain as active component for the hydrogenation of furfural. Increasing the thickness of the ALD-generated overcoats restricts the adsorption of furfural onto the step sites of Pd NPs and increases the selectivity to furan. Furan selectivities and furfural conversions are linearly correlated for samples with or without an overcoating, though the slopes differ. The ALD technique can tune the selectivity of furfural hydrogenation over Pd NPs and has improved our understanding of the reaction mechanism. The above conclusions are further supported by density functional theory (DFT) calculations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of Sphagnum farming on the greenhouse gas balance of donor and propagation areas, irrigation polders and commercial cultivation sites

NASA Astrophysics Data System (ADS)

Oestmann, Jan; Tiemeyer, Bärbel

2017-04-01

Drainage of peatlands for agriculture, forestry and peat extraction turned these landscapes into hotspots of greenhouse gas emissions. Climate protection now fosters rewetting projects to restore the natural peatland function as a sink of atmospheric carbon. One possible way to combine ecological and economical goals is Sphagnum farming, i.e. the cultivation of Sphagnum mosses as high-quality substrates for horticulture. This project scientifically evaluates the attempt of commercial Sphagnum farming on former peat extraction sites in north-western Germany. The exchange of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) of the whole peatland-based production chain comprising a donor mire, a propagation area, an irrigation polder and a cultivation site will be determined in a high temporal resolution for two years using manual chambers. This will allow evaluating the greenhouse gas balance of Sphagnum farming sites in comparison to near-natural sites and the potential of Sphagnum farming for restoring drained peatlands to sinks of atmospheric carbon. The influence of different irrigation techniques will also be tested. Additionally, selected plots will be equipped with open top chambers in order to examine the greenhouse gas exchange under potential future climate change conditions. Finally, a 13C pulse labeling experiment will make it possible to trace the newly sequestered CO2 in biomass, soil, respiration and dissolved organic carbon.

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering.

PubMed

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-21

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

PubMed Central

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-01-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

NASA Astrophysics Data System (ADS)

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

PubMed

Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

2014-12-10

Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

CCS Activities Being Performed by the U.S. DOE

PubMed Central

Dressel, Brian; Deel, Dawn; Rodosta, Traci; Plasynski, Sean; Litynski, John; Myer, Larry

2011-01-01

The United States Department of Energy (DOE) is the lead federal agency for the development and deployment of carbon sequestration technologies. Its mission includes promoting scientific and technological innovations and transfer of knowledge for safe and permanent storage of CO2 in the subsurface. To accomplish its mission, DOE is characterizing and classifying potential geologic storage reservoirs in basins throughout the U.S. and Canada, and developing best practices for project developers, to help ensure the safety of future geologic storage projects. DOE’s Carbon Sequestration Program, Regional Carbon Sequestration Partnership (RCSP) Initiative, administered by the National Energy Technology Laboratory (NETL), is identifying, characterizing, and testing potential injection formations. The RCSP Initiative consists of collaborations among government, industry, universities, and international organizations. Through this collaborative effort, a series of integrated knowledge-based tools have been developed to help potential sequestration project developers. They are the Carbon Sequestration Atlas of the United States and Canada, National Carbon Sequestration Database and Geographic System (NATCARB), and best practice manuals for CCS including Depositional Reservoir Classification for CO2; Public Outreach and Education for Carbon Storage Projects; Monitoring, Verification, and Accounting of CO2 Stored in Deep Geologic Formation; Site Screening, Site Selection, and Initial Characterization of CO2 Storage in Deep Geologic Formations. DOE’s future research will help with refinement of these tools and additional best practice manuals (BPM) which focus on other technical aspects of project development. PMID:21556188

Surface Engineering of a Supported PdAg Catalyst for Hydrogenation of CO2 to Formic Acid: Elucidating the Active Pd Atoms in Alloy Nanoparticles.

PubMed

Mori, Kohsuke; Sano, Taiki; Kobayashi, Hisayoshi; Yamashita, Hiromi

2018-06-22

The hydrogenation of carbon dioxide (CO 2 ) to formic acid (FA; HCOOH), a renewable hydrogen storage material, is a promising means of realizing an economical CO 2 -mediated hydrogen energy cycle. The development of reliable heter-ogeneous catalysts is an urgent yet challenging task associated with such systems, although precise catalytic site design protocols are still lacking. In the present study, we demonstrate that PdAg alloy nanoparticles (NPs) supported on TiO 2 promote the efficient selective hydrogenation of CO 2 to give FA even under mild reaction conditions (2.0 MPa, 100 °C). Specimens made using surface engineering with atomic precision reveal a strong correlation between increased cata-lytic activity and decreased electron density of active Pd atoms resulting from a synergistic effect of alloying with Ag atoms. The isolated and electronically promoted surface-exposed Pd atoms in Pd@Ag alloy NPs exhibit a maximum turnover number of 14,839 based on the quantity of surface Pd atoms, which represents a more than ten-fold increase compared to the activity of monometallic Pd/TiO 2 . Kinetic and density functional theory (DFT) calculations show that the attack on the C atom in HCO 3 - by a dissociated H atom over an active Pd site is the rate-determining step during this reaction, and this step is boosted by PdAg alloy NPs having a low Pd/Ag ratio.

The influence of calcination temperatures on the acid-based properties and catalytic activity for the 1,3-butadiene synthesis from ethanol/acetaldehyde mixture

NASA Astrophysics Data System (ADS)

Gao, Meixiang; Jiang, Haoxi; Zhang, Minhua

2018-05-01

The influences of the calcination temperature on the catalysts' acid-based properties and catalytic activity for the 1,3-butadiene synthesis from ethanol are investigated. The results show that the 2 wt% ZrO2/Nano-SiO2 calcined at 773 K shows the best performance with the selectivity of 93.18% and conversion of 58.52% when reacted at 593 K, a WHSV of 1.8 h-1 and 3.5:1 volume ratio ethanol-to-acetaldehyde in an atmospheric fixed-bed reactor. Prepared catalysts were characterized by N2 adsorption-desorption, XRD, temperature-programmed desorption of NH3 and CO2, FTIR spectroscopy of adsorbed pyridine and CO2. Based on the relationship between the catalyst activity and its properties, the fact can be presumed that the formation and strength of Zrsbnd Osbnd Si bond determines the acid-based properties of the catalyst. In addition, moderate-intensity weak acid-basic sites are more suitable for ethanol conversion to BD with the amount of acid and basic sites as close as possible.

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

Environmental controls of temporal and spatial variability in CO2 and CH4 fluxes in a neotropical peatland.

PubMed

Wright, Emma L; Black, Colin R; Turner, Benjamin L; Sjögersten, Sofie

2013-12-01

Tropical peatlands play an important role in the global storage and cycling of carbon (C) but information on carbon dioxide (CO2) and methane (CH4) fluxes from these systems is sparse, particularly in the Neotropics. We quantified short and long-term temporal and small scale spatial variation in CO2 and CH4 fluxes from three contrasting vegetation communities in a domed ombrotrophic peatland in Panama. There was significant variation in CO2 fluxes among vegetation communities in the order Campnosperma panamensis > Raphia taedigera > Cyperus. There was no consistent variation among sites and no discernible seasonal pattern of CH4 flux despite the considerable range of values recorded (e.g. -1.0 to 12.6 mg m(-2) h(-1) in 2007). CO2 fluxes varied seasonally in 2007, being greatest in drier periods (300-400 mg m(-2) h(-1)) and lowest during the wet period (60-132 mg m(-2) h(-1)) while very high emissions were found during the 2009 wet period, suggesting that peak CO2 fluxes may occur following both low and high rainfall. In contrast, only weak relationships between CH4 flux and rainfall (positive at the C. panamensis site) and solar radiation (negative at the C. panamensis and Cyperus sites) was found. CO2 fluxes showed a diurnal pattern across sites and at the Cyperus sp. site CO2 and CH4 fluxes were positively correlated. The amount of dissolved carbon and nutrients were strong predictors of small scale within-site variability in gas release but the effect was site-specific. We conclude that (i) temporal variability in CO2 was greater than variation among vegetation communities; (ii) rainfall may be a good predictor of CO2 emissions from tropical peatlands but temporal variation in CH4 does not follow seasonal rainfall patterns; and (iii) diurnal variation in CO2 fluxes across different vegetation communities can be described by a Fourier model. © 2013 John Wiley & Sons Ltd.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Li, Zhenjun; Chen, Long

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupymore » the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.« less

Anti-site defected MoS2 sheet for catalytic application

NASA Astrophysics Data System (ADS)

Sharma, Archana; Husain, Mushahid; Khan, Mohd. Shahid

2018-04-01

To prevent harmful and poisonous CO gas molecules, catalysts are needed for converting them into benign substances. Density functional theory (DFT) calculations have been used to investigate CO oxidation on the surface of MoS2 monolayer with Mo atom embedded at S-vacancy site (anti-site defect). The stronger interaction between Mo metal with O2 molecule as compared with CO molecule suggests high catalytic activity. The complete oxidation of CO is studied in a two-step procedure using Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms with a low overall energy barrier of 0.35 eV. Creation of anti-site defect makes the surface of MoS2 nanosheet catalytically active for the CO oxidation to take place.

A NMDA receptor glycine site partial agonist, GLYX-13, simultaneously enhances LTP and reduces LTD at Schaffer collateral-CA1 synapses in hippocampus.

PubMed

Zhang, Xiao-lei; Sullivan, John A; Moskal, Joseph R; Stanton, Patric K

2008-12-01

N-methyl-D-aspartate glutamate receptors (NMDARs) are a key route for Ca2+ influx into neurons important to both activity-dependent synaptic plasticity and, when uncontrolled, triggering events that cause neuronal degeneration and death. Among regulatory binding sites on the NMDAR complex is a glycine binding site, distinct from the glutamate binding site, which must be co-activated for NMDAR channel opening. We developed a novel glycine site partial agonist, GLYX-13, which is both nootropic and neuroprotective in vivo. Here, we assessed the effects of GLYX-13 on long-term synaptic plasticity and NMDAR transmission at Schaffer collateral-CA1 synapses in hippocampal slices in vitro. GLYX-13 simultaneously enhanced the magnitude of long-term potentiation (LTP) of synaptic transmission, while reducing long-term depression (LTD). GLYX-13 reduced NMDA receptor-mediated synaptic currents in CA1 pyramidal neurons evoked by low frequency Schaffer collateral stimulation, but enhanced NMDAR currents during high frequency bursts of activity, and these actions were occluded by a saturating concentration of the glycine site agonist d-serine. Direct two-photon imaging of Schaffer collateral burst-evoked increases in [Ca2+] in individual dendritic spines revealed that GLYX-13 selectively enhanced burst-induced NMDAR-dependent spine Ca2+ influx. Examining the rate of MK-801 block of synaptic versus extrasynaptic NMDAR-gated channels revealed that GLYX-13 selectively enhanced activation of burst-driven extrasynaptic NMDARs, with an action that was blocked by the NR2B-selective NMDAR antagonist ifenprodil. Our data suggest that GLYX-13 may have unique therapeutic potential as a learning and memory enhancer because of its ability to simultaneously enhance LTP and suppress LTD.

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

PubMed Central

Li, Jinghui; Chen, Zhuo; Umar, Ahmad; Liu, Yang; Shang, Ying; Zhang, Xiaokai; Wang, Yao

2017-01-01

Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed. PMID:28051190

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

NASA Astrophysics Data System (ADS)

Li, Jinghui; Chen, Zhuo; Umar, Ahmad; Liu, Yang; Shang, Ying; Zhang, Xiaokai; Wang, Yao

2017-01-01

Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed.

Mesoscale carbon sequestration site screening and CCS infrastructure analysis.

PubMed

Keating, Gordon N; Middleton, Richard S; Stauffer, Philip H; Viswanathan, Hari S; Letellier, Bruce C; Pasqualini, Donatella; Pawar, Rajesh J; Wolfsberg, Andrew V

2011-01-01

We explore carbon capture and sequestration (CCS) at the meso-scale, a level of study between regional carbon accounting and highly detailed reservoir models for individual sites. We develop an approach to CO(2) sequestration site screening for industries or energy development policies that involves identification of appropriate sequestration basin, analysis of geologic formations, definition of surface sites, design of infrastructure, and analysis of CO(2) transport and storage costs. Our case study involves carbon management for potential oil shale development in the Piceance-Uinta Basin, CO and UT. This study uses new capabilities of the CO(2)-PENS model for site screening, including reservoir capacity, injectivity, and cost calculations for simple reservoirs at multiple sites. We couple this with a model of optimized source-sink-network infrastructure (SimCCS) to design pipeline networks and minimize CCS cost for a given industry or region. The CLEAR(uff) dynamical assessment model calculates the CO(2) source term for various oil production levels. Nine sites in a 13,300 km(2) area have the capacity to store 6.5 GtCO(2), corresponding to shale-oil production of 1.3 Mbbl/day for 50 years (about 1/4 of U.S. crude oil production). Our results highlight the complex, nonlinear relationship between the spatial deployment of CCS infrastructure and the oil-shale production rate.

A Highly Selective and Robust Co(II)-Based Homogeneous Catalyst for Reduction of CO2 to CO in CH3CN/H2O Solution Driven by Visible Light.

PubMed

Ouyang, Ting; Hou, Cheng; Wang, Jia-Wei; Liu, Wen-Ju; Zhong, Di-Chang; Ke, Zhuo-Feng; Lu, Tong-Bu

2017-07-03

Visible-light driven reduction of CO 2 into chemical fuels has attracted enormous interest in the production of sustainable energy and reversal of the global warming trend. The main challenge in this field is the development of efficient, selective, and economic photocatalysts. Herein, we report a Co(II)-based homogeneous catalyst, [Co(NTB)CH 3 CN](ClO 4 ) 2 (1, NTB = tris(benzimidazolyl-2-methyl)amine), which shows high selectivity and stability for the catalytic reduction of CO 2 to CO in a water-containing system driven by visible light, with turnover number (TON) and turnover frequency (TOF) values of 1179 and 0.032 s -1 , respectively, and selectivity to CO of 97%. The high catalytic activity of 1 for photochemical CO 2 -to-CO conversion is supported by the results of electrochemical investigations and DFT calculations.

On the Structure-Property Relationships of Cation-Exchanged ZK-5 Zeolites for CO 2 Adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Trong D.; Hudson, Matthew R.; Brown, Craig M.

2017-02-16

The CO 2 adsorption properties of cation-exchanged Li-, Na-, K-, and Mg-ZK-5 zeolites were correlated to the molecular structures determined by Rietveld refinements of synchrotron powder X-ray diffraction patterns. Li-, K-, and Na-ZK-5 all exhibited high isosteric heats of adsorption (Qst) at low CO 2 coverage, with Na-ZK-5 having the highest Qst (ca. 49 kJ mol -1). Mg2+ was located at the center of the zeolite hexagonal prism with the cation inaccessible to CO 2, leading to a much lower Qst (ca. 30 kJ mol-1) and lower overall uptake capacity. Multiple CO 2 adsorption sites were identified at a givenmore » CO 2 loading amount for all four cation-exchanged ZK-5 adsorbents. Site A at the flat eight-membered ring windows and site B/B* in the γ-cages were the primary adsorption sites in Li - and Na-ZK-5 zeolites. Relatively strong dual-cation adsorption sites contributed significantly to an enhanced electrostatic interaction for CO 2 in all ZK-5 samples. This interaction gives rise to a migration of Li + and Mg 2+ cations from their original locations at the center of the hexagonal prisms toward the α-cages, in which they interact more strongly with the adsorbed CO 2.« less

Carbon Dioxide and CO2 Isotopes at Three Spatial Scales Over the Rocky Mountains

NASA Astrophysics Data System (ADS)

Bowling, D. R.; Schaeffer, S. M.; Miller, J. B.; Stephens, B. B.

2006-12-01

Recent studies highlight the importance of western mountain regions to the North American carbon sink, suggesting 25 to 50 percent of the U.S. sink can be attributed to montane ecosystems. Isotopes of CO2 provide insight into ecosystem carbon cycling, plant physiological processes, and atmospheric boundary-layer dynamics, and are useful in integration of processes over multiple scales. CO2 isotopes have played a central role in our understanding of the magnitude and inter-annual dynamics of the terrestrial carbon sink at a variety of spatial and temporal scales, and will be crucial to understanding the carbon balance and carbon accounting of the North American continent. In 2005, we began a long-term study examining biosphere- atmosphere exchange of CO2 and its stable isotopes over the Rocky Mountains in Colorado. Measurements are made at 3 sites representing 3 different spatial scales. These include a subalpine forest site (3050 m elevation, the Niwot Ridge AmeriFlux site), a tundra site 3 km away (3520 m, representing the overlying forest air), and an aircraft site 125 km to the northeast over the plains (vertical profiles from ground level at 1740 m to 8000 m, representing the regional convective boundary layer and the free troposphere). The tundra (NWR) and aircraft (CAR) sites have been part of NOAA/CCGG Cooperative Air Sampling Network for many years. Observed CO2 and δ13C showed seasonal variation (> 10 ppm and >0.5 permil) and strong local variation at all sites (>100 ppm and >5 permil at the forest site). The forest exerted a strong respiratory influence on the overlying air during the fall and winter. Measurements 10m above the top of the forest canopy in winter were always higher in CO2 (~ 3 ppm) and more negative in δ13C of CO2 ~ 0.3 permil) than those at the tundra site. Summer data are still being analyzed, but we expect this to shift in the other direction during the growing season. Substantial synoptic variation in CO2 and δ13C was observed at all three sites, sometimes with simultaneous changes at all sites, sometimes not. The diurnal and seasonal patterns of CO2 and δ13C at the three sites will be discussed, and these data will be used to assess the local variability of the long-term CO2 (since 1968) and δ13C (since 1990) record at Niwot Ridge.

CO2 sorption on surface-modified carbonaceous support: Probing the influence of the carbon black microporosity and surface polarity

NASA Astrophysics Data System (ADS)

Gargiulo, Valentina; Alfè, Michela; Ammendola, Paola; Raganati, Federica; Chirone, Riccardo

2016-01-01

The use of solid sorbents is a convenient option in post-combustion CO2 capture strategies. Sorbents selection is a key point because the materials are required to be both low-cost and versatile in typical post-combustion conditions in order to guarantee an economically advantageous overall process. This work compares strategies to tailor the chemico-physical features of carbon black (CB) by surface-modification and/or coating with a CO2-sorbent phase. The influence of the CB microporosity, enhanced by chemical/thermal treatments, is also taken into account. Three CB surface modifications are performed and compared: (i) oxidation and functionalization with amino-groups, (ii) coating with iron oxides and (iii) impregnation with an ionic liquid (IL). The CO2 capture performance is evaluated on the basis of the breakthrough curves measured at atmospheric pressure and room temperature in a lab-scale fixed bed micro-reactor. Most of tested solids adsorb a CO2 amount significantly higher than a 13X zeolite and DARCO FGD (Norit) activated carbon (up to 4 times more in the best case). The sorbents bearing basic functionalities (amino-groups and IL) exhibit the highest CO2 sorption capacity. The use of a microporous carbonaceous support limits the accessibility of CO2 toward the adsorbing phase (IL or FM) lowering the number of accessible binding sites for CO2.

Conserving Critical Sites for Biodiversity Provides Disproportionate Benefits to People

PubMed Central

Larsen, Frank W.; Turner, Will R.; Brooks, Thomas M.

2012-01-01

Protecting natural habitats in priority areas is essential to halt the loss of biodiversity. Yet whether these benefits for biodiversity also yield benefits for human well-being remains controversial. Here we assess the potential human well-being benefits of safeguarding a global network of sites identified as top priorities for the conservation of threatened species. Conserving these sites would yield benefits – in terms of a) climate change mitigation through avoidance of CO2 emissions from deforestation; b) freshwater services to downstream human populations; c) retention of option value; and d) benefits to maintenance of human cultural diversity – significantly exceeding those anticipated from randomly selected sites within the same countries and ecoregions. Results suggest that safeguarding sites important for biodiversity conservation provides substantial benefits to human well-being. PMID:22666337

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide

PubMed Central

Bae, Hyeonhu; Park, Minwoo; Jang, Byungryul; Kang, Yura; Park, Jinwoo; Lee, Hosik; Chung, Haegeun; Chung, ChiHye; Hong, Suklyun; Kwon, Yongkyung; Yakobson, Boris I.; Lee, Hoonkyung

2016-01-01

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10−3 bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc– or V–porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials. PMID:26902156

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide.

PubMed

Bae, Hyeonhu; Park, Minwoo; Jang, Byungryul; Kang, Yura; Park, Jinwoo; Lee, Hosik; Chung, Haegeun; Chung, ChiHye; Hong, Suklyun; Kwon, Yongkyung; Yakobson, Boris I; Lee, Hoonkyung

2016-02-23

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10(-3) bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc- or V-porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials.

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide

NASA Astrophysics Data System (ADS)

Bae, Hyeonhu; Park, Minwoo; Jang, Byungryul; Kang, Yura; Park, Jinwoo; Lee, Hosik; Chung, Haegeun; Chung, Chihye; Hong, Suklyun; Kwon, Yongkyung; Yakobson, Boris I.; Lee, Hoonkyung

2016-02-01

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10-3 bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc- or V-porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials.

Influence of oxygen-, nitrogen-, and sulfur-containing compounds on the hydrodeoxygenation of phenols over sulfided CoMo/[gamma]-Al[sub 2]O[sub 3] and NiMo/[gamma]-Al[sub 2]O[sub 3] catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laurent, E.; Delmon, B.

1993-11-01

The hydrodeoxygenation (HDO) of phenols is a key reaction of the hydroprocessing of bio-oils, because phenolic molecules represent an important part of these oils and they are among the most difficult to deoxygenate. This reaction is also a very good reaction test for the characterization of the hydrogenation and hydrogenolysis functions of hydrotreating catalysts. In this work, the influence of competitors on the activity and selectivity of 4-methylphenol HDO over conventional CoMo and NiMo hydrotreating catalysts was evaluated in batch reaction tests. The inhibiting strength followed the order H[sub 2]O << 2-ethylphenol < H[sub 2]S < NH[sub 3]. In allmore » cases, the hydrogenolysis path was more inhibited than the hydrogenation path, indicating a higher adsorption strength and electrophilicity of associated sites. The inhibition was quantified according to a Langmuir adsorption concept. The deviations from this model were attributed to a distribution of the adsorption strength. As opposed to other competitors, hydrogen sulfide slightly promotes the hydrogenation activity of CoMo but not of NiMo. These observations were interpreted as the result of an interconversion of the hydrogenolysis and hydrogenation active sites.« less

The Ketzin Project, Germany - Status and Future of the First European on-shore CO2 Storage Site

NASA Astrophysics Data System (ADS)

Kuehn, M.; Martens, S.; Moeller, F.; Lueth, S.; Liebscher, A.; Kempka, T.; Ketzin Group

2010-12-01

At the Ketzin site close to Berlin, the German Research Centre for Geosciences operates Europe’s first on-shore CO2 storage site with the aim of increasing the understanding of geological storage of CO2 in saline aquifers. Following site characterization and drilling of three wells, the in-situ field laboratory is fully in use since the CO2 injection started in June 2008. Our presentation summarizes key results from the first (Schilling et al. 2009) and second year (Martens et al. 2010) of injection and outlines future activities. Focus of the research is on interdisciplinary monitoring and modeling approaches. Since start of the CO2 injection on June 30, 2008, the injection facility has been reliably and safely operated. By the end of August 2010, about 37,700 tons of food grade CO2 have been injected into a sandstone aquifer of the Triassic Stuttgart Formation at a depth of about 630 to 700 m. The new project CO2MAN (CO2 Reservoir Management) is planned to succeed the EU-funded CO2SINK project which ended in March 2010 and further nationally funded projects. Our interdisciplinary monitoring concept for the Ketzin site integrates geophysical, geochemical and microbial investigations. Following baseline measurements prior to the injection, repeat measurements have been carried out for a comprehensive characterization of the reservoir and the developing CO2 plume. CO2MAN aims at continuing the injection up to a maximum of 100,000 tons of CO2, advancing the monitoring concept and further integrating numerical modeling. Planned activities include the installation of a third and a fourth observation well and the testing of well abandonment procedures. All data available from the Ketzin wells and the different monitoring techniques are going to be compiled into an integral geological model of the site. Such a geological model is the prerequisite for any holistic approach and understanding of CO2 storage not only at Ketzin. A variety of seismic methods, including cross-hole measurement between both observation wells, surface-downhole observations, and 2D and 3D surface surveys have been used in order to cover the near-injection to regional scale. In addition, geoelectric methods including cross-hole measurements between the wells and additional surface and surface-downhole electrical resistivity tomography have been applied to monitor the CO2 migration process. Geological modeling and dynamic flow modeling is conducted in different phases, including pre-existing data, information obtained from drilling and subsequent CO2 injection. On-going modeling also integrates recent geophysical monitoring data in order to improve the understanding of geological heterogeneities at the Ketzin site and their impact on the CO2 plume distribution. Martens S., Liebscher A., Möller F., Würdemann H, Schilling F., Kühn M., and Ketzin Group (2010) Progress Report on the First European on-shore CO2 Storage Site at Ketzin (Germany) - Second Year of Injection, GHGT 10, subm. Schilling F., Borm G., Würdemann H., Möller F., Kühn M., CO2SINK Group (2009) Status Report on the First European on-shore CO2 Storage Site at Ketzin (Germany). GHGT 9, Energy Procedia 1(1) 2029-2035, doi: 10.1016/j.egypro.2009.01.264

Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion.

PubMed

Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

2016-05-01

A highly porous metal-organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn2 (COO)4 ) and tetrameric (Zn4 (O)(CO2 )6 ), is successfully assembled by the reaction of a tricarboxylate ligand with Zn(II) ion. Subsequently, single-crystal-to-single-crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu(II) and Co(II) ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation-exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu(II) and Co(II) exchanged samples exhibit comparable CO2 adsorption capability to the pristine Zn(II) -based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO2 with epoxides into related carbonates demonstrate that Zn(II) -based MOF affords the highest catalytic activity as compared with Cu(II) and Co(II) exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient CO2 capture by functionalized graphene oxide nanosheets as fillers to fabricate multi-permselective mixed matrix membranes.

PubMed

Li, Xueqin; Cheng, Youdong; Zhang, Haiyang; Wang, Shaofei; Jiang, Zhongyi; Guo, Ruili; Wu, Hong

2015-03-11

A novel multi-permselective mixed matrix membrane (MP-MMM) is developed by incorporating versatile fillers functionalized with ethylene oxide (EO) groups and an amine carrier into a polymer matrix. The as-prepared MP-MMMs can separate CO2 efficiently because of the simultaneous enhancement of diffusivity selectivity, solubility selectivity, and reactivity selectivity. To be specific, MP-MMMs were fabricated by incorporating polyethylene glycol- and polyethylenimine-functionalized graphene oxide nanosheets (PEG-PEI-GO) into a commercial low-cost Pebax matrix. The PEG-PEI-GO plays multiple roles in enhancing membrane performance. First, the high-aspect ratio GO nanosheets in a polymer matrix increase the length of the tortuous path of gas diffusion and generate a rigidified interface between the polymer matrix and fillers, enhancing the diffusivity selectivity. Second, PEG consisting of EO groups has excellent affinity for CO2 to enhance the solubility selectivity. Third, PEI with abundant primary, secondary, and tertiary amine groups reacts reversibly with CO2 to enhance reactivity selectivity. Thus, the as-prepared MP-MMMs exhibit excellent CO2 permeability and CO2/gas selectivity. The MP-MMM doped with 10 wt % PEG-PEI-GO displays optimal gas separation performance with a CO2 permeability of 1330 Barrer, a CO2/CH4 selectivity of 45, and a CO2/N2 selectivity of 120, surpassing the upper bound lines of the Robeson study of 2008 (1 Barrer = 10(-10) cm(3) (STP) cm(-2) s(-1) cm(-1) Hg).

CO2 dispersion modelling over Paris region within the CO2-MEGAPARIS project

NASA Astrophysics Data System (ADS)

Lac, C.; Donnelly, R. P.; Masson, V.; Pal, S.; Riette, S.; Donier, S.; Queguiner, S.; Tanguy, G.; Ammoura, L.; Xueref-Remy, I.

2013-05-01

Accurate simulation of the spatial and temporal variability of tracer mixing ratios over urban areas is a challenging and interesting task needed to be performed in order to utilise CO2 measurements in an atmospheric inverse framework and to better estimate regional CO2 fluxes. This study investigates the ability of a high-resolution model to simulate meteorological and CO2 fields around Paris agglomeration during the March field campaign of the CO2-MEGAPARIS project. The mesoscale atmospheric model Meso-NH, running at 2 km horizontal resolution, is coupled with the Town Energy Balance (TEB) urban canopy scheme and with the Interactions between Soil, Biosphere and Atmosphere CO2-reactive (ISBA-A-gs) surface scheme, allowing a full interaction of CO2 modelling between the surface and the atmosphere. Statistical scores show a good representation of the urban heat island (UHI) with stronger urban-rural contrasts on temperature at night than during the day by up to 7 °C. Boundary layer heights (BLH) have been evaluated on urban, suburban and rural sites during the campaign, and also on a suburban site over 1 yr. The diurnal cycles of the BLH are well captured, especially the onset time of the BLH increase and its growth rate in the morning, which are essential for tall tower CO2 observatories. The main discrepancy is a small negative bias over urban and suburban sites during nighttime (respectively 45 m and 5 m), leading to a few overestimations of nocturnal CO2 mixing ratios at suburban sites and a bias of +5 ppm. The diurnal CO2 cycle is generally well captured for all the sites. At the Eiffel tower, the observed spikes of CO2 maxima occur every morning exactly at the time at which the atmospheric boundary layer (ABL) growth reaches the measurement height. At suburban ground stations, CO2 measurements exhibit maxima at the beginning and at the end of each night, when the ABL is fully contracted, with a strong spatio-temporal variability. A sensitivity test without urban parameterisation removes the UHI and underpredicts nighttime BLH over urban and suburban sites, leading to large overestimation of nocturnal CO2 mixing ratio at the suburban sites (bias of +17 ppm). The agreement between observation and prediction for BLH and CO2 concentrations and urban-rural increments, both day and night, demonstrates the potential of using the urban mesoscale system in the context of inverse modelling

Diffusional flux of CO2 through snow: Spatial and temporal variability among alpine-subalpine sites

Treesearch

Richard A. Sommerfeld; William J. Massman; Robert C. Musselman

1996-01-01

Three alpine and three subalpine sites were monitored for up to 4 years to acquire data on the temporal and spatial variability of CO2 flux through snowpacks. We conclude that the snow formed a passive cap which controlled the concentration of CO2 at the snow-soil interface, while the flux of CO2 into the atmosphere was controlled by CO2 production in the soil....

Waterbird nest-site selection is influenced by neighboring nests and island topography

USGS Publications Warehouse

Hartman, Christopher; Ackerman, Joshua T.; Takekawa, John Y.; Herzog, Mark

2016-01-01

Avian nest-site selection is influenced by factors operating across multiple spatial scales. Identifying preferred physical characteristics (e.g., topography, vegetation structure) can inform managers to improve nesting habitat suitability. However, social factors (e.g., attraction, territoriality, competition) can complicate understanding physical characteristics preferred by nesting birds. We simultaneously evaluated the physical characteristics and social factors influencing selection of island nest sites by colonial-nesting American avocets (Recurvirostra americana) and Forster's terns (Sterna forsteri) at 2 spatial scales in San Francisco Bay, 2011–2012. At the larger island plot (1 m2) scale, we used real-time kinematics to produce detailed topographies of nesting islands and map the distribution of nests. Nesting probability was greatest in island plots between 0.5 m and 1.5 m above the water surface, at distances <10 m from the water's edge, and of moderately steep (avocets) or flat (terns) slopes. Further, avocet and tern nesting probability increased as the number of nests initiated in adjacent plots increased up to a peak of 11–12 tern nests, and then decreased thereafter. Yet, avocets were less likely to nest in plots adjacent to plots with nesting avocets, suggesting an influence of intra-specific territoriality. At the smaller microhabitat scale, or the area immediately surrounding the nest, we compared topography, vegetation, and distance to nearest nest between nest sites and paired random sites. Topography had little influence on selection of the nest microhabitat. Instead, nest sites were more likely to have vegetation present, and greater cover, than random sites. Finally, avocet, and to a lesser extent tern, nest sites were closer to other active conspecific or heterospecific nests than random sites, indicating that social attraction played a role in selection of nest microhabitat. Our results demonstrate key differences in nest-site selection between co-occurring avocets and terns, and indicate the effects of physical characteristics and social factors on selection of nesting habitat are dependent on the spatial scale examined. Moreover, these results indicate that islands with abundant area between 0.5 m and 1.5 m above the water surface, within 10 m of the water's edge, and containing a mosaic of slopes ranging from flat to moderately steep would provide preferred nesting habitat for avocets and terns. © 2016 The Wildlife Society.

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

PubMed

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

Gas separation mechanism of CO 2 selective amidoxime-poly(1-trimethylsilyl-1-propyne) membranes

DOE PAGES

Feng, Hongbo; Hong, Tao; Mahurin, Shannon Mark; ...

2017-05-09

Polymeric membranes for CO 2 separation have drawn significant attention in academia and industry. We prepared amidoxime-functionalized poly(1-trimethylsilyl-1-propyne) (AO-PTMSP) membranes through hydrosilylation and post-polymerization modification. Compared to neat PTMSP membranes, the AO-PTMSP membranes showed significant enhancements in CO 2/N 2 gas separation performance (CO 2 permeability ~6000 Barrer; CO 2/N 2 selectivity 17). This systematic study provides clear guidelines on how to tune the CO 2-philicity within PTMSP matrices and the effects on gas selectivity. Key parameters for elucidating the gas transport mechanism were discussed based on CO 2 sorption measurements and fractional free volume estimates. The effect of themore » AO content on CO 2/N 2 selectivity was further examined by means of density functional theory calculations. Here, both experimental and theoretical data provide consistent results that conclusively show that CO 2/N 2 separation performance is enhanced by increased CO 2 polymer interactions.« less

Gas separation mechanism of CO 2 selective amidoxime-poly(1-trimethylsilyl-1-propyne) membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Hongbo; Hong, Tao; Mahurin, Shannon Mark

Polymeric membranes for CO 2 separation have drawn significant attention in academia and industry. We prepared amidoxime-functionalized poly(1-trimethylsilyl-1-propyne) (AO-PTMSP) membranes through hydrosilylation and post-polymerization modification. Compared to neat PTMSP membranes, the AO-PTMSP membranes showed significant enhancements in CO 2/N 2 gas separation performance (CO 2 permeability ~6000 Barrer; CO 2/N 2 selectivity 17). This systematic study provides clear guidelines on how to tune the CO 2-philicity within PTMSP matrices and the effects on gas selectivity. Key parameters for elucidating the gas transport mechanism were discussed based on CO 2 sorption measurements and fractional free volume estimates. The effect of themore » AO content on CO 2/N 2 selectivity was further examined by means of density functional theory calculations. Here, both experimental and theoretical data provide consistent results that conclusively show that CO 2/N 2 separation performance is enhanced by increased CO 2 polymer interactions.« less

Solubility trapping in formation water as dominant CO(2) sink in natural gas fields.

PubMed

Gilfillan, Stuart M V; Lollar, Barbara Sherwood; Holland, Greg; Blagburn, Dave; Stevens, Scott; Schoell, Martin; Cassidy, Martin; Ding, Zhenju; Zhou, Zheng; Lacrampe-Couloume, Georges; Ballentine, Chris J

2009-04-02

Injecting CO(2) into deep geological strata is proposed as a safe and economically favourable means of storing CO(2) captured from industrial point sources. It is difficult, however, to assess the long-term consequences of CO(2) flooding in the subsurface from decadal observations of existing disposal sites. Both the site design and long-term safety modelling critically depend on how and where CO(2) will be stored in the site over its lifetime. Within a geological storage site, the injected CO(2) can dissolve in solution or precipitate as carbonate minerals. Here we identify and quantify the principal mechanism of CO(2) fluid phase removal in nine natural gas fields in North America, China and Europe, using noble gas and carbon isotope tracers. The natural gas fields investigated in our study are dominated by a CO(2) phase and provide a natural analogue for assessing the geological storage of anthropogenic CO(2) over millennial timescales. We find that in seven gas fields with siliciclastic or carbonate-dominated reservoir lithologies, dissolution in formation water at a pH of 5-5.8 is the sole major sink for CO(2). In two fields with siliciclastic reservoir lithologies, some CO(2) loss through precipitation as carbonate minerals cannot be ruled out, but can account for a maximum of 18 per cent of the loss of emplaced CO(2). In view of our findings that geological mineral fixation is a minor CO(2) trapping mechanism in natural gas fields, we suggest that long-term anthropogenic CO(2) storage models in similar geological systems should focus on the potential mobility of CO(2) dissolved in water.

Atomistic study on the site preference and lattice vibration of Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} (T=Al and Ge)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Hai-Xia; Wang, Xiao-Xu; Department of Materials Engineering, National Ping Tung University of Technology and Science, Ping-Tung 91201, Taiwan

The effects of the Y substitution for Gd on the structural stability and the site preference of intermetallics Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} (T=Al and Ge) are studied by using a series of interatomic pair potentials. The calculated results show Y can stabilize Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} with the tetragonal structure, and Y substitute for Gd with a strong preference for the 2b sites. The calculated lattice parameters are in good agreement with the experimental data. Furthermore, the total and partial phonon densities of states are evaluated for the Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} compounds withmore » the tetragonal structure. A qualitative analysis is carried out with the relevant potentials for the vibrational modes, which makes it possible to predict some properties related to lattice vibration. - Graphical abstract: The lattice cell of Gd{sub 3}Co{sub 29}T{sub 4}B{sub 10} consists of 92 atoms, or two Gd{sub 3}Co{sub 29}T{sub 4}B{sub 10} formula units, with fourteen distinct kinds of site. Rare-earth atoms occupy 2b and 4d sites, Co atoms occupy the Co1(2c), Co2(8i1), Co3(8i2), Co4(8i3), Co5(8j1), Co6(8j2) and Co7(16k), T atoms occupy the T(8i) sites, and B atoms occupy the B1(2c1), B2(2c2), B3(8i) and B4(8j) sites. - Highlights: • The application of the pair potentials obtained from lattice-inversion method. • The lattice vibrations for Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} (T=Ge and Al) are first evaluated. • The Y atoms should prefer the 2b site of Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} compounds. • The total and partial phonon densities of states are evaluated for the Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} compounds with the tetragonal structure. • A qualitative analysis is carried out with the relevant potentials for the vibrational modes.« less

Cretaceous paleoceanography of the western North Atlantic Ocean

USGS Publications Warehouse

Arthur, Michael A.; Dean, Walter E.

1986-01-01

In this paper we summarize available information on the Cretaceous lithostratigraphy and paleoceanography of the western North Atlantic. The data and some of our interpretations draw in large part on papers published in the Deep Sea Drilling Project (DSDP) volumes. We have attempted to cite relevant references when possible, but space limitations make it difficult to give proper credit to all sources; we apologize for any omissions.Organic carbon (Corg) and carbonate (CaCO3) analyses were tabulated for each site from papers in the DSDP Initial Report volumes and other published works (e.g., Summerhayes,1981). Corg, CaCO3, and non-CaCO3 mass accumulation rates (MARS) were calculated using core by core averages of component percentages for the more continuously cored sites; core averages for wet bulk density and porosity (from DSDP data files); biostratigraphies of de Graciansky and others (1982), Roth and Bowdler (1981), and Cool (1982); and the time scales of the Decade of North American Geology (Palmer, 1983; Kent and Gradstein, this volume) or Harland and others (1982; see Plate 1).Backtracked paleodepths for western North Atlantic DSDP Sites from Tucholke and Vogt (1979) with the revised stratigraphy of de Graciansky and others (1982) were used in plotting Corg and CaCO3 in Figures 2, 3, 4 and 5 (see also Thierstein, 1979).Backtracking curves of seafloor paleodepth versus age (Sclater and others, 1977; Tucholke and Vogt, 1979) for selected western North Atlantic DSDP sites. Average CaCO3 concentrations per core are shown by code number

Direct and Selective Synthesis of Hydrogen Peroxide over Palladium-Tellurium Catalysts at Ambient Pressure.

PubMed

Tian, Pengfei; Xu, Xingyan; Ao, Can; Ding, Doudou; Li, Wei; Si, Rui; Tu, Weifeng; Xu, Jing; Han, Yi-Fan

2017-09-11

Highly selective hydrogen peroxide (H 2 O 2 ) synthesis directly from H 2 and O 2 is a strongly desired reaction for green processes. Herein a highly efficient palladium-tellurium (Pd-Te/TiO 2 ) catalyst with a selectivity of nearly 100 % toward H 2 O 2 under mild conditions (283 K, 0.1 MPa, and a semi-batch continuous flow reactor) is reported. The size of Pd particles was remarkably reduced from 2.1 nm to 1.4 nm with the addition of Te. The Te-modified Pd surface could significantly weaken the dissociative activation of O 2 , leading to the non-dissociative hydrogenation of O 2 . Density functional theory calculations illuminated the critical role of Te in the selective hydrogenation of O 2 , in that the active sites composed of Pd and Te could significantly restrain side reactions. This work has made significant progress on the development of high-selectivity catalysts for the direct synthesis of H 2 O 2 at ambient pressure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the properties of metal–organic framework nodes as supports of single-site iridium catalysts: node modification by atomic layer deposition of aluminium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Dong; Momeni, Mohammad R.; Demir, Hakan

The metal–organic framework NU-1000, with Zr 6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH 3) 2(iso-propoxide)] 2followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C 2H 4) 2(acac) (acac = acetylacetonate) and converted to Ir(CO) 2complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly,more » the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.« less

Carbon dioxide (hydrogen sulfide) membrane separations and WGS membrane reactor modeling for fuel cells

NASA Astrophysics Data System (ADS)

Huang, Jin

Acid-gas removal is of great importance in many environmental or energy-related processes. Compared to current commercial technologies, membrane-based CO2 and H2S capture has the advantages of low energy consumption, low weight and space requirement, simplicity of installation/operation, and high process flexibility. However, the large-scale application of the membrane separation technology is limited by the relatively low transport properties. In this study, CO2 (H2S)-selective polymeric membranes with high permeability and high selectivity have been studied based on the facilitated transport mechanism. The membrane showed facilitated effect for both CO2 and H2S. A CO2 permeability of above 2000 Barrers, a CO2/H2 selectivity of greater than 40, and a CO2/N2 selectivity of greater than 200 at 100--150°C were observed. As a result of higher reaction rate and smaller diffusing compound, the H2S permeability and H2S/H2 selectivity were about three times higher than those properties for CO2. The novel CO2-selective membrane has been applied to capture CO 2 from flue gas and natural gas. In the CO2 capture experiments from a gas mixture with N2 and H2, a permeate CO 2 dry concentration of greater than 98% was obtained by using steam as the sweep gas. In CO2/CH4 separation, decent CO 2 transport properties were obtained with a feed pressure up to 500 psia. With the thin-film composite membrane structure, significant increase on the CO2 flux was achieved with the decrease of the selective layer thickness. With the continuous removal of CO2, CO2-selective water-gas-shift (WGS) membrane reactor is a promising approach to enhance CO conversion and increase the purity of H2 at process pressure under relatively low temperature. The simultaneous reaction and transport process in the countercurrent WGS membrane reactor was simulated by using a one-dimensional non-isothermal model. The modeling results show that a CO concentration of less than 10 ppm and a H2 recovery of greater than 97% are achievable from reforming syngases. In an experimental study, the reversible WGS was shifted forward by removing CO2 so that the CO concentration was significantly decreased to less than 10 ppm. The modeling results agreed well with the experimental data.

Structural and surface properties of CuO-ZnO-Cr{sub 2}O{sub 3} catalysts and their relationship with selectivity to higher alcohol synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campos-Martin, J.M.; Fierro, J.L.G.; Guerrero-Ruiz, A.

1995-10-01

A series of copper-zinc-chromium catalysts of different compositions and calcination temperatures has been prepared, characterized by several techniques (BET specific surface area, XRD, gravimetric TPR, TPD-CO, and XPS), and tested under high alcohol synthesis (HAS) conditions. CO hydrogenation was carried out at reaction temperatures of 523-598 K and 50 bar total pressure. The influence of catalyst composition, calcination temperature, and surface characteristics on the HAS selectivity was studied. The optimum HAS yields were found in the low Cr content region, but chromium was needed. Although chromium oxide does not seem to be involved in the catalytic site, its presence inmore » the catalyst composition is essential, owing to the larger specific surfaces and catalyst stability obtained at the highest reaction temperatures. For low Cr content composition, the temperature-programmed reduction (TPR) profiles were shifted to higher temperatures and simultaneously larger CO{sub 2} amounts were found in the temperature-programmed desorption profiles of adsorbed CO (TPD-CO). Photoelectron spectra (XPS) revealed that the oxidation state of copper is Cu{sup 2+} in the calcined catalysts and Cu{sup O} in the reduced ones; Cu{sup +} was only stabilized in a CuCr{sub 2}O{sub 4} spinel in the Cr-rich catalysts. These features derived from catalyst characterization are discussed in the framework of the catalytic behaviour for HAS synthesis. 53 refs., 7 figs., 4 tabs.« less

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

DOE PAGES

Kneebone, Jared L.; Daifuku, Stephanie L.; Kehl, Jeffrey A.; ...

2017-07-06

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O 2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O 2 or O 2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe activemore » sites in complex ORR catalysts that combines an effective probe molecule (NO (g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO (g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO (g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO (g) probe molecules. Moreover, such sites are likely also reactive to O 2, possibly serving as the ORR active sites in the synthesized materials.« less

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kneebone, Jared L.; Daifuku, Stephanie L.; Kehl, Jeffrey A.

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O 2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O 2 or O 2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe activemore » sites in complex ORR catalysts that combines an effective probe molecule (NO (g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO (g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO (g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO (g) probe molecules. Moreover, such sites are likely also reactive to O 2, possibly serving as the ORR active sites in the synthesized materials.« less

Anion-Exchange Membrane Fuel Cells with Improved CO2 Tolerance: Impact of Chemically Induced Bicarbonate Ion Consumption.

PubMed

Katayama, Yu; Yamauchi, Kosuke; Hayashi, Kohei; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Kikkawa, Yuuki; Negishi, Takayuki; Watanabe, Shin; Isomura, Takenori; Eguchi, Koichi

2017-08-30

Over the last few decades, because of the significant development of anion exchange membranes, increasing efforts have been devoted the realization of anion exchange membrane fuel cells (AEMFCs) that operate with the supply of hydrogen generated on-site. In this paper, ammonia was selected as a hydrogen source, following which the effect of conceivable impurities, unreacted NH 3 and atmospheric CO 2 , on the performance of AEMFCs was established. As expected, we show that these impurities worsen the performance of AEMFCs significantly. Furthermore, with the help of in situ attenuated total reflection infrared (ATR-IR) spectroscopy, it was revealed that the degradation of the cell performance was primarily due to the inhibition of the hydrogen oxidation reaction (HOR). This is attributed to the active site occupation by CO-related adspecies derived from (bi)carbonate adspecies. Interestingly, this degradation in the HOR activity is suppressed in the presence of both NH 3 and HCO 3 - because of the bicarbonate ion consumption reaction induced by the existence of NH 3 . Further analysis using in situ ATR-IR and electrochemical methods revealed that the poisonous CO-related adspecies were completely removed under NH 3 -HCO 3 - conditions, accompanied by the improvement in HOR activity. Finally, a fuel cell test was conducted by using the practical AEMFC with the supply of NH 3 -contained H 2 gas to the anode and ambient air to the cathode. The result confirmed the validity of this positive effect of NH 3 -HCO 3 - coexistence on CO 2 -tolerence of AEMFCs. The cell performance achieved nearly 95% of that without any impurity in the fuels. These results clearly show the impact of the chemically induced bicarbonate ion consumption reaction on the realization of highly CO 2 -tolerent AEMFCs.

Evaluation of the Effect of the CO2 Ocean Sequestration on Marine Life in the Sea near Japan Using a Numerical Model

NASA Astrophysics Data System (ADS)

Nakamura, Tomoaki; Wada, Akira; Hasegawa, Kazuyuki; Ochiai, Minoru

CO2 oceanic sequestration is one of the technologies for reducing the discharge of CO2 into the atmosphere, which is considered to cause the global warming, and consists in isolating industry-made CO2 gas within the depths of the ocean. This method is expected to enable industry-made CO2 to be separated from the atmosphere for a considerably long period of time. On the other hand, it is also feared that the CO2 injected in the ocean may lower pH of seawater surrounding the sequestration site, thus may adversely affect marine organisms. For evaluating the biological influences, we have studied to precisely predict the CO2 distribution around the CO2 injection site by a numerical simulation method. In previous studies, in which a 2 degree by 2 degree mesh was employed in the simulation, CO2 concentrations tended to be evenly dispersed within the grid, giving lower concentration values. Thus, the calculation accuracy within the area several hundred kilometers from the CO2 injection site was not satisfactory for the biological effect assessment. In the present study, we improved the accuracy of concentration distribution by changing the computational mesh resolution for a 0.2 by 0.2 degree. By the renewed method we could obtain detailed CO2 distribution in waters within several hundred kilometers of the injection site, and clarified that the Moving-ship procedure may have less effects of lowered pH on marine organisms than the fixed-point release procedure of CO2 sequestration.

Structural identification of Zn xZr yO z catalysts for Cascade aldolization and self-deoxygenation reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor

Complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH3/CO2 temperature programmed desorption (NH3/CO2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn2+more » and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO2, caused by steam reforming. The incorporation of atomic Zn2+ into the ZrO2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., ). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C3=-C6=) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Structural Identification of Zn xZr yO z Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH 3/CO 2 temperature programmed desorption (NH 3/CO 2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO 2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn 2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO 2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn 2+ and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO 2, caused by steam reforming. The incorporation of atomic Zn 2+ into the ZrO 2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO 2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—omore » $$\\curvearrowleft\\atop{e\\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C 3 =-C 6 =) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Structural Identification of Zn xZr yO z Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

DOE PAGES

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor; ...

2018-04-22

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH 3/CO 2 temperature programmed desorption (NH 3/CO 2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO 2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn 2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO 2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn 2+ and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO 2, caused by steam reforming. The incorporation of atomic Zn 2+ into the ZrO 2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO 2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—omore » $$\\curvearrowleft\\atop{e\\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C 3 =-C 6 =) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Strong metal-support interactions

NASA Technical Reports Server (NTRS)

Vannice, M. Albert

1987-01-01

It has been demonstrated that synergistic metal-support effects can occur which markedly enhance specific activity and alter selectivity in certain reactions. Because of the presence of such effects in certain reactions conducted under reducing conditions (that is, under H2 pressure), but not others, the creation of unique sites at the metal-support interface seems to be the best model at the present time to explain this behavior. The postulation of these sites, which are specific for a certain reactant such as CO, provides an effective explanation for the higher methanation rates that have been reported over some catalysts. The creation of these sites in the adlineation zone is facilitated by hydrogen spillover from the metal surface, and this same process can also enhance the reduction of many oxide supports. Although oxygen spillover is much less probable due to its higher heat of adsorption, it is much less well understood and the possibility of rate enhancements in CO oxidation caused by special interface sites cannot be discounted at the present time. Consequently, this seems to be an important area of future research.

Contrasting impact of forestry-drainage on CO2 balance at two adjacent peatlands in Finland

NASA Astrophysics Data System (ADS)

Lohila, Annalea; Minkkinen, Kari; Penttilä, Timo; Launiainen, Samuli; Koskinen, Markku; Ojanen, Paavo; Laurila, Tuomas

2014-05-01

Fate of carbon in peatlands after drainage has been a subject of many studies, particularly at agriculturally managed sites, but also at sites prepared for forestry. In general, the drainage of peatlands has been considered to trigger the decomposition rate of peat and to cause carbon dioxide (CO2) emissions from the peat into the atmosphere. However, there is not yet full consensus on what are the main regulating factors of the carbon balances in forested peatlands, and do all the forested peatland even act as a source of carbon into the atmosphere. In this study we compare the CO2 exchange rates at two adjacent peatland sites in southern Finland, drained for forestry about 40 years earlier. The pair of sites with similar climatic conditions offer an excellent case for studying the mechanisms controlling the carbon balances of forestry-drained peatlands. The sites differ from each other only by fertility, which has an impact on, e.g., tree growth rate. At both sites, CO2 and energy fluxes have been measured with the eddy covariance method over the course of 4 years, but not simultaneously. We have also built at both sites an automatic system consisting of six transparent closed chambers which collect data on the CO2 exchange of the forest floor vegetation (including tree roots) and soil around the year. This enables us to quantify the carbon uptake potential of the ground layer and the peat decomposition rates and helps us to understand the differences between the sites. The results show that the pine and dwarf-shrub-dominated site (nutrient-poor) is a large CO2 sink. The site with a mixture of spruce, birch and pine and lesser ground vegetation (nutrient-rich), on the contrary, has a close-to-neutral CO2 balance, despite the much higher tree growth rate there. In this presentation we will compare the general dynamics and climatic responses of CO2 exchange at the sites, compare the magnitude and factors causing interannual variation, and discuss potential reasons for the different carbon balances.

Effects of 15% CO/sub 2/ on the accumulation of the phytoalexin phaseollin in Phaseolus vulgaris in response to mechanical injury and to infection by Colletotrichum lindemuthianum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, R.M.; Rahe, J.E.

1977-04-15

Accumulation of phaseollin at sites of point-freezing injury on etiolated hypocotyls of Phaseolus vulgaris occurred in air but was prevented when seedlings were placed in air containing 15 percent CO/sub 2/ immediately after injury. The inhibitory effect was partially overcome when CO/sub 2/-treated seedlings were returned to air. Phaseollin accumulation in 15 percent CO/sub 2/ did occur, however, when injured seedlings were maintained in air for 3-9 h before being transferred to CO/sub 2/, indicating that the sensitivity to CO/sub 2/ lies at an early stage of the process leading to phaseollin production. In contrast, phaseollin accumulation at sites ofmore » infection of P. vulgaris by an incompatible race of Colletotrichum lindemuthianum was not inhibited by 15 percent CO/sub 2/. These results indicate that the processes leading to the accumulation of phaseollin at incompatible infection sites and at injury sites may be regulated differently.« less

Photosynthetic biomineralization of radioactive Sr via microalgal CO2 absorption.

PubMed

Lee, Seung Yeop; Jung, Kwang-Hwan; Lee, Ju Eun; Lee, Keon Ah; Lee, Sang-Hyo; Lee, Ji Young; Lee, Jae Kwang; Jeong, Jong Tae; Lee, Seung-Yop

2014-11-01

Water-soluble radiostrontium ((90)Sr) was efficiently removed as a carbonate form through microalgal photosynthetic process. The immobilization of soluble (90)Sr radionuclide and production of highly-precipitable radio-strontianite ((90)SrCO3) biomineral are achieved by using Chlorella vulgaris, and the biologically induced mineralization drastically decreased the (90)Sr radioactivity in water to make the highest (90)Sr removal ever reported. The high-resolution microscopy revealed that the short-term removal of soluble (90)Sr by C. vulgaris was attributable to the rapid and selective carbonation of (90)Sr together with the consumption of dissolved CO2 during photosynthesis. A small amount of carbonate in water could act as Sr(2+) sinks through the particular ability of the microalga to make the carbonate mineral of Sr stabilized firmly at the surface site. Copyright © 2014 Elsevier Ltd. All rights reserved.

Trends in stomatal density and 13C/12C ratios of Pinus flexilis needles during last glacial-interglacial cycle

USGS Publications Warehouse

Van De Water, Peter K.; Leavitt, Steven W.; Betancourt, J.L.

1994-01-01

Measurements of stomatal density and ?? 13C of limber pine (Pinus flexilis) needles (leaves) preserved in pack rat middens from the Great Basin reveal shifts in plant physiology and leaf morphology during the last 30,000 years. Sites were selected so as to offset glacial to Holocene climatic differences and thus to isolate the effects of changing atmospheric CO2 levels. Stomatal density decreased ~17 percent and ?? 13C decreased ~1.5 per mil during deglaciation from 15,000 to 12,000 years ago, concomitant with a 30 percent increase in atmospheric CO2. Water-use efficiency increased ~15 percent during deglaciation, if temperature and humidity were held constant and the proxy values for CO2 and ?? 13C of past atmospheres are accurate. The ??13C variations may help constrain hypotheses about the redistribution of carbon between the atmosphere and biosphere during the last glacial-interglacial cycle.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rychel, Dwight

The Permian Basin Carbon Capture, Utilization and Storage (CCUS) Training Center was one of seven regional centers formed in 2009 under the American Recovery and Reinvestment Act of 2009 and managed by the Department of Energy. Based in the Permian Basin, it is focused on the utilization of CO 2 Enhanced Oil Recovery (EOR) projects for the long term storage of CO 2 while producing a domestic oil and revenue stream. It delivers training to students, oil and gas professionals, regulators, environmental and academia through a robust web site, newsletter, tech alerts, webinars, self-paced online courses, one day workshops, andmore » two day high level forums. While course material prominently features all aspects of the capture, transportation and EOR utilization of CO 2, the audience focus is represented by its high level forums where selected graduate students with an interest in CCUS interact with Industry experts and in-house workshops for the regulatory community.« less

Vapor-phase catalytic oxidesulfurization (ODS) of organosulfur compounds over supported metal oxide catalysts

NASA Astrophysics Data System (ADS)

Choi, Sukwon

Sulfur in transportation fuels remains a leading source of SOx emissions from vehicle engines and is a major source of air pollution. The very low levels of sulfur globally mandated for transportation fuels in the near future cannot be achieved by current practices of hydrodesulfurization (HDS) for sulfur removal, which operate under severe conditions (high T, P) and use valuable H2. Novel vapor-phase catalytic oxidesulfurization (ODS) processes of selectively oxidizing various organosulfur compounds (carbonyl sulfide, carbon disulfide, methanethiol, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), thiophene, 2,5-dimenthylthiophene) typically found in various industrial streams (e.g., petroleum refining, pulp and paper) into valuable chemical intermediates (H 2CO, CO, H2, maleic anhydride and concentrated SO2) has been extensively studied. This research has primarily focused on establishing the fundamental kinetics and mechanisms of these selective oxidation reactions over well-defined supported metal oxide catalysts. The selective oxidation reactions of COS + O2 → CO + SO2; 2CS2 + 5O2 → 2CO + 4SO2; CH3SH + 2O 2 → H2CO + SO2 + H2O; C4 H4S + 3O2 → C4H2O 3 + H2O + SO2; were studied. Raman spectroscopy revealed that the supported metal oxide phases were 100% dispersed on the oxide substrate. All the catalysts were highly active and selective for the oxidesulfurization of carbonyl sulfide, carbon disulfide, methanethiol, and thiophene between 290--330°C, 230--270°C, 350--400°C, and 250--400°C, respectively and did not deactivate. The TOFs (turnover frequency, normalized activity per active catalytic site) for all ODS reactions over supported vanadia catalysts, only containing molecularly dispersed surface vanadia species, varied within one order of magnitude and revealed the V-O-Support bridging bond was involved in the critical rate-determining kinetic steps. The surface reaction mechanism for each reaction was revealed by in situ IR (infrared) and temperature programmed surface reaction-mass spectroscopy (TPSR-MS). The systematic investigation of vapor-phase oxidesulfurization (ODS) reactions of organosulfur compounds over catalytic supported metal oxides revealed the facile S-O exchange mechanisms allow for the efficient removal of sulfur while producing value-added chemicals and represents the discovery of a new series of catalytic reactions.

Geomechanical Modeling for Improved CO2 Storage Security

NASA Astrophysics Data System (ADS)

Rutqvist, J.; Rinaldi, A. P.; Cappa, F.; Jeanne, P.; Mazzoldi, A.; Urpi, L.; Vilarrasa, V.; Guglielmi, Y.

2017-12-01

This presentation summarizes recent modeling studies on geomechanical aspects related to Geologic Carbon Sequestration (GCS,) including modeling potential fault reactivation, seismicity and CO2 leakage. The model simulations demonstrates that the potential for fault reactivation and the resulting seismic magnitude as well as the potential for creating a leakage path through overburden sealing layers (caprock) depends on a number of parameters such as fault orientation, stress field, and rock properties. The model simulations further demonstrate that seismic events large enough to be felt by humans requires brittle fault properties as well as continuous fault permeability allowing for the pressure to be distributed over a large fault patch to be ruptured at once. Heterogeneous fault properties, which are commonly encountered in faults intersecting multilayered shale/sandstone sequences, effectively reduce the likelihood of inducing felt seismicity and also effectively impede upward CO2 leakage. Site specific model simulations of the In Salah CO2 storage site showed that deep fractured zone responses and associated seismicity occurred in the brittle fractured sandstone reservoir, but at a very substantial reservoir overpressure close to the magnitude of the least principal stress. It is suggested that coupled geomechanical modeling be used to guide the site selection and assisting in identification of locations most prone to unwanted and damaging geomechanical changes, and to evaluate potential consequence of such unwanted geomechanical changes. The geomechanical modeling can be used to better estimate the maximum sustainable injection rate or reservoir pressure and thereby provide for improved CO2 storage security. Whether damaging geomechanical changes could actually occur very much depends on the local stress field and local reservoir properties such the presence of ductile rock and faults (which can aseismically accommodate for the stress and strain induced by the injection) or, on the contrary, the presence of more brittle faults that, if critically stressed for shear, might be more prone to induce felt seismicity.

Sizable dynamics in small pores: CO2 location and motion in the α-Mg formate metal-organic framework.

PubMed

Lu, Yuanjun; Lucier, Bryan E G; Zhang, Yue; Ren, Pengju; Zheng, Anmin; Huang, Yining

2017-02-22

Metal-organic frameworks (MOFs) are promising materials for carbon dioxide (CO 2 ) adsorption and storage; however, many details regarding CO 2 dynamics and specific adsorption site locations within MOFs remain unknown, restricting the practical uses of MOFs for CO 2 capture. The intriguing α-magnesium formate (α-Mg 3 (HCOO) 6 ) MOF can adsorb CO 2 and features a small pore size. Using an intertwined approach of 13 C solid-state NMR (SSNMR) spectroscopy, 1 H- 13 C cross-polarization SSNMR, and computational molecular dynamics (MD) simulations, new physical insights and a rich variety of information have been uncovered regarding CO 2 adsorption in this MOF, including the surprising suggestion that CO 2 motion is restricted at elevated temperatures. Guest CO 2 molecules undergo a combined localized rotational wobbling and non-localized twofold jumping between adsorption sites. MD simulations and SSNMR experiments accurately locate the CO 2 adsorption sites; the mechanism behind CO 2 adsorption is the distant interaction between the hydrogen atom of the MOF formate linker and a guest CO 2 oxygen atom, which are ca. 3.2 Å apart.

Synthesis, characterization, and application of Zn(NH 3)(CO3) for selective adsorptive separation of CO2

NASA Astrophysics Data System (ADS)

Khazeni, Naasser

This study explores the potential of Zn(NH3)(CO3) for selective CO2 separation. It develops a novel, highly controllable, single-pot synthesis approach based on urea hydrolysis and solvothermal aging to increase the feasibility of synthesizing Zn(NH3)(CO3), determines the structure of Zn(NH3)(CO3) in detail through single crystal X-ray diffraction and powder X-ray diffraction analyses, and performs adsorption analyses for the compound using CO2, N 2, H2, O2, and CH4 as adsorptives. Through adsorptive characterization, a systematic adsorbent selection screening is performed to assess the potential application of Zn(NH3)(CO 3) for adsorptive separation of CO2 from an upstream gas mixture of power generation, hydrogen production, and natural gas industries. Structural analysis shows Zn(NH3)(CO3) to have an inorganic helical framework that consists of a small helix of (ZnOCO) 2 and a large helix of (ZnOCO)4 with two ammines (NH 3) pendant from every other zinc. In terms of adsorption capacity and CO2 selectivity, Zn(NH3)(CO3) adsorbed 0.550 mmole/g CO2 at 293 K and 4500 mmHg, but only 0.047 mmole/g N 2, 0.084 mmole/g H2, 0.207 mmole/g 02, and 0.060 mmole/g CH4 at the same temperature and pressure. This behavior demonstrates considerable equilibrium selectivities - 36, 31, 63, and 11 - for separating CO2 from CH4, CO2 from H 2, CO2 from N2, and CO2 from 02, respectively. During adsorption, the pendant ammines act as the gates of check-valves: applied pressure opens the gates for adsorption; and during desorption, the gates are closed, trapping the adsorbates, until a reduction of pressure to near-atmospheric levels. Therefore, Zn(NH3)(CO3) exhibits low-pressure H3 or H4 hysteresis, indicating that the Zn(NH3)(CO3) framework can achieve gas storage at near-atmospheric pressures. Additionally, the compound proves structurally stable, with an adsorption decrease of 0.8% after 20 adsorption/desorption cycles - a factor that, considered with the other characteristics of Zn(NH3)(CO 3), renders this compound a potential candidate for separating CO 2 from H2and N2. The adsorbent selection screening affirmed that Zn(NH3)(CO 3) can be a potential candidate for LFG separation using PSA, LFG separation using VSA, oxy-fuel CO2 purification using PSA, and air separation using PSA at 263K. For those applications, the low CO2 uptake by Zn(NH3)(CO3) was offset by considerable selectivity, regenerability, and adsorbent selection parameter.

Completion of five years of safe CO2 injection and transition into the post-closure phase at the Ketzin pilot site

NASA Astrophysics Data System (ADS)

Martens, Sonja; Moeller, Fabian; Streibel, Martin; Liebscher, Axel; Ketzin Group

2014-05-01

The injection of CO2 at the Ketzin pilot site in Germany ended after five years in August 2013. We present the key results from site operation and outline future activities within the post-closure phase. From June 2008 onwards, a total amount of 67 kt of CO2 was safely injected into a saline aquifer (Upper Triassic sandstone) at a depth of 630 m - 650 m. The CO2 used was mainly of food grade quality (purity > 99.9%). In addition, 1.5 kt of CO2 from the pilot capture facility "Schwarze Pumpe" (power plant CO2 with purity > 99.7%) was injected in 2011. During regular operation, the CO2 was pre-heated on-site to 45°C before injection in order to avoid pressure build-up within the reservoir. During the final months of injection a "cold-injection" experiment with a stepwise decrease of the injection temperature down to 10°C was conducted between March and July 2013. In summer 2013, the injection of a mixture of 95% CO2 and 5% N2 was also tested. After ceasing the injection in August the injection facility and pipeline were removed in December 2013. Geological storage of CO2 at the Ketzin pilot site has so far proceeded in a safe and reliable manner. As a result of one of the most comprehensive R&D programs worldwide, a combination of different geochemical and geophysical monitoring methods is able to detect even small quantities of CO2 and map their spatial extent. After the cessation of CO2 injection a series of activities and further investigations are involved in the post-closure phase. The aim is that Ketzin will for the first time ever close the complete life-time cycle of a CO2 storage site at pilot scale. The five wells (1 injection/observation well, 4 pure observation wells) will be successively abandoned within the next few years while monitoring is continuing. The partial plugging of one observation well in the reservoir section was already completed in fall 2013. The new four-years project COMPLETE (CO2 post-injection monitoring and post-closure phase at the Ketzin pilot site) started in January 2014. Activities within COMPLETE include R&D work on well integrity, post-closure monitoring as well as two field experiments. One is a back-production test of the CO2 aiming at information on the physicochemical properties of the back-produced CO2 as well as the pressure response of the reservoir. The other experiment will focus on brine injection into the CO2 storage reservoir in order to study e.g. the residual gas saturation. Public outreach has been a key element for the project from the very beginning and accompanies the research on CO2 storage at Ketzin since 2004. Thus dissemination (e.g. www.co2ketzin.de) and activities at the visitor centre at the pilot site will continue within COMPLETE and along the entire life cycle of the Ketzin project.

Structural characterization of framework–gas interactions in the metal–organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction† †Electronic supplementary information (ESI) available: Supplementary figures, crystallographic information, adsorption isotherms and fits, CCDC 1530119–1530126. For ESI and crystallographic data in CIF or other electronic format. See DOI: 10.1039/c7sc00449d Click here for additional data file. Click here for additional data file.

PubMed Central

Gonzalez, Miguel I.; Mason, Jarad A.; Bloch, Eric D.; Teat, Simon J.; Gagnon, Kevin J.; Morrison, Gregory Y.; Queen, Wendy L.

2017-01-01

The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH4, N2, O2, Ar, and P4 adsorption in Co2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH4 and Co–Ar interactions observed in Co2(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co2(dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol–1 (for Ar). Moreover, the structures of Co2(dobdc)·3.8N2, Co2(dobdc)·5.9O2, and Co2(dobdc)·2.0Ar reveal the location of secondary (N2, O2, and Ar) and tertiary (O2) binding sites in Co2(dobdc), while high-pressure CO2, CO, CH4, N2, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures. PMID:28966783

Porous NiCo2O4 nanoarray-integrated binder-free 3D open electrode offers a highly efficient sensing platform for enzyme-free glucose detection.

PubMed

Luo, X; Huang, M; He, D; Wang, M; Zhang, Y; Jiang, P

2018-05-29

High electrical conductivity and the exposure to more active sites are crucial to boost the performance of a glucose sensor. A porous binary metal oxide nanoarray integrated on a binder-free 3D electrode is expected to offer a highly sensitive sensing platform. As a model, porous NiCo2O4 nanowire arrays supported on carbon cloth (NiCo2O4 NWA/CC) have been prepared and used for enzyme-free glucose sensing. NiCo2O4 NWA/CC shows larger effective surface area, superior electronic conductivity, and higher catalytic activity towards enzyme-free glucose sensing, with a linear range from 1 μM to 0.63 mM, a sensitivity of 4.12 mA mM-1 cm-2, and low detection limit of 0.5 μM. Moreover, NiCo2O4 NWA/CC also displays good selectivity and stability and thus, it can be reliable for glucose detection in human serum samples. These findings inspire the fabrication of a high-performance electrochemical sensing platform by preparing porous binary metal oxide nanoarrays supported on a 3D conductive substrate.

Mixed matrix membranes with fast and selective transport pathways for efficient CO2 separation

NASA Astrophysics Data System (ADS)

Hou, Jinpeng; Li, Xueqin; Guo, Ruili; Zhang, Jianshu; Wang, Zhongming

2018-03-01

To improve CO2 separation performance, porous carbon nanosheets (PCNs) were used as a filler into a Pebax MH 1657 (Pebax) matrix, fabricating mixed matrix membranes (MMMs). The PCNs exhibited a preferential horizontal orientation within the Pebax matrix because of the extremely large 2D plane and nanoscale thickness of the matrix. Therefore, the micropores of the PCNs provided fast CO2 transport pathways, which led to increased CO2 permeability. The reduced pore size of the PCNs was a consequence of the overlapping of PCNs and the polymer chains penetrating into the pores of the PCNs. The reduction in the pore size of the PCNs improved the CO2/gas selectivity. As a result, the CO2 permeability and CO2/CH4 selectivity of the Pebax membrane with 10 wt% PCNs-loading (Pebax-PCNs-10) were 520 barrer and 51, respectively, for CO2/CH4 mixed-gas. The CO2 permeability and CO2/N2 selectivity of the Pebax-PCNs-10 membrane were 614 barrer and 61, respectively, for CO2/N2 mixed-gas.

The co-crystal structure of ubiquitin carboxy-terminal hydrolase L1 (UCHL1) with a tripeptide fluoromethyl ketone (Z-VAE(OMe)-FMK)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davies, Christopher W.; Chaney, Joseph; Korbel, Gregory

2012-07-25

UCHL1 is a 223 amino acid member of the UCH family of deubiquitinating enzymes (DUBs), found abundantly and exclusively expressed in neurons and the testis in normal tissues. Two naturally occurring variants of UCHL1 are directly involved in Parkinson's disease (PD). Not only has UCHL1 been linked to PD, but it has oncogenic properties, having been found abnormally expressed in lung, pancreatic, and colorectal cancers. Although inhibitors of UCHL1 have been described previously the co-crystal structure of the enzyme bound to any inhibitor has not been reported. Herein, we report the X-ray structure of UCHL1 co-crystallized with a peptide-based fluoromethylketonemore » inhibitor, Z-VAE(OMe)-FMK (VAEFMK) at 2.35 {angstrom} resolution. The co-crystal structure reveals that the inhibitor binds in the active-site cleft, irreversibly modifying the active-site cysteine; however, the catalytic histidine is still misaligned as seen in the native structure, suggesting that the inhibitor binds to an inactive form of the enzyme. Our structure also reveals that the inhibitor approaches the active-site cleft from the opposite side of the crossover loop as compared to the direction of approach of ubiquitin's C-terminal tail, thereby occupying the P1{prime} (leaving group) site, a binding site perhaps used by the unknown C-terminal extension of ubiquitin in the actual in vivo substrate(s) of UCHL1. This structure provides a view of molecular contacts at the active-site cleft between the inhibitor and the enzyme as well as furnishing structural information needed to facilitate further design of inhibitors targeted to UCHL1 with high selectivity and potency.« less

Greenhouse gas exchange of rewetted bog peat extraction sites and a Sphagnum cultivation site in northwest Germany

NASA Astrophysics Data System (ADS)

Beyer, C.; Höper, H.

2015-04-01

During the last decades an increasing area of drained peatlands has been rewetted. Especially in Germany, rewetting is the principal treatment on cutover sites when peat extraction is finished. The objectives are bog restoration and the reduction of greenhouse gas (GHG) emissions. The first sites were rewetted in the 1980s. Thus, there is a good opportunity to study long-term effects of rewetting on greenhouse gas exchange, which has not been done so far on temperate cutover peatlands. Moreover, Sphagnum cultivating may become a new way to use cutover peatlands and agriculturally used peatlands as it permits the economical use of bogs under wet conditions. The climate impact of such measures has not been studied yet. We conducted a field study on the exchange of carbon dioxide, methane and nitrous oxide at three rewetted sites with a gradient from dry to wet conditions and at a Sphagnum cultivation site in NW Germany over the course of more than 2 years. Gas fluxes were measured using transparent and opaque closed chambers. The ecosystem respiration (CO2) and the net ecosystem exchange (CO2) were modelled at a high temporal resolution. Measured and modelled values fit very well together. Annually cumulated gas flux rates, net ecosystem carbon balances (NECB) and global warming potential (GWP) balances were determined. The annual net ecosystem exchange (CO2) varied strongly at the rewetted sites (from -201.7 ± 126.8 to 29.7± 112.7g CO2-C m-2 a-1) due to differing weather conditions, water levels and vegetation. The Sphagnum cultivation site was a sink of CO2 (-118.8 ± 48.1 and -78.6 ± 39.8 g CO2-C m-2 a-1). The annual CH4 balances ranged between 16.2 ± 2.2 and 24.2 ± 5.0g CH4-C m-2 a-1 at two inundated sites, while one rewetted site with a comparatively low water level and the Sphagnum farming site show CH4 fluxes close to 0. The net N2O fluxes were low and not significantly different between the four sites. The annual NECB was between -185.5 ± 126.9 and 49.9 ± 112.8 g CO2-C m-2 a-1 at the rewetted sites and -115.8 ± 48.1 and -77 ± 39.8 g CO2-C m-2 a-1 at the Sphagnum cultivating site. The annual GWP100 balances ranged from -280.5 ± 465.2 to 644.5 ± 413.6 g CO2-eq. m-2 a-1 at the rewetted sites. In contrast, the Sphagnum farming site had a cooling impact on the climate in both years (-356.8 ± 176.5 and -234.9 ± 145.9 g CO2-C m-2 a-1). If the carbon exported through the harvest of the Sphagnum biomass and the additional CO2 emission from the decay of the organic material is considered, the NECB and GWP100 balances are near neutral. Peat mining sites are likely to become net carbon sinks and a peat accumulating ("growing") peatland within 30 years of rewetting, but the GWP100 balance may still be positive. A recommended measure for rewetting is to achieve a water level of a few centimetres below ground. Sphagnum farming is a climate-friendly alternative to conventional commercial use of bogs. A year-round constant water level of a few centimetres below ground level should be maintained.

Atmospheric CO2 Records from Sites Operated by the Fraunhofer Institute for Atmospheric Environment Research (1978 - 1992)

DOE Data Explorer

Sladkovic, R. [Fraunhofer Institute for Atmospheric Environmental Research (IFU), Garmisch-Partenkirchen, Germany; Scheel, H. E. [Fraunhofer Institute for Atmospheric Environmental Research (IFU), Garmisch-Partenkirchen, Germany; Seiler, W. [Fraunhofer Institute for Atmospheric Environmental Research (IFU), Garmisch-Partenkirchen, Germany

1997-01-01

The monitoring site at Garmisch-Partenkirchen is considered a grassland valley site. Because of strong local influence (vegetation and meteorology), the CO2 concentrations at Garmisch-Partenkirchen are higher and show greater seasonal amplitudes than the concentrations measured at Wank or Zugspitze. According to the filtered data, the annual atmospheric CO2 concentrations at Garmisch-Partenkirchen increased from 330.2 ppmv in 1978 to 345.1 ppmv in 1986 and from 347.6 ppmv in 1988 to 354.7 ppmv in 1992. The monitoring site at Wank Peak (WMO-BAPMoN station) is located on the grass-covered, rounded top of the mountain, just above the timberline. The mean annual CO2 concentrations at Wank Peak increased from 334.2 ppmv in 1980 to 348.6 ppmv in 1992. The station at Zugspitze is located near the summit of the highest mountain of the German Alps. In 1990, the site of CO2 sampling was changed from a location 250 m below the summit to a new monitoring station (2937 m above MSL) close to the mountain top. Compatibility of the results was seen from measurements conducted in parallel at the two sites for several months. Because of the high elevation of the mountain station, the CO2 measurements at Zugspitze can be considered free of regional contamination most of the time. The mean annual CO2 concentrations at Zugspitze increased from 333.7 ppmv in 1981 to 349.4 ppmv in 1992.

Geospatial variability of soil CO2-C exchange in the main terrestrial ecosystems of Keller Peninsula, Maritime Antarctica.

PubMed

Thomazini, A; Francelino, M R; Pereira, A B; Schünemann, A L; Mendonça, E S; Almeida, P H A; Schaefer, C E G R

2016-08-15

Soils and vegetation play an important role in the carbon exchange in Maritime Antarctica but little is known on the spatial variability of carbon processes in Antarctic terrestrial environments. The objective of the current study was to investigate (i) the soil development and (ii) spatial variability of ecosystem respiration (ER), net ecosystem CO2 exchange (NEE), gross primary production (GPP), soil temperature (ST) and soil moisture (SM) under four distinct vegetation types and a bare soil in Keller Peninsula, King George Island, Maritime Antarctica, as follows: site 1: moss-turf community; site 2: moss-carpet community; site 3: phanerogamic antarctic community; site 4: moss-carpet community (predominantly colonized by Sanionia uncinata); site 5: bare soil. Soils were sampled at different layers. A regular 40-point (5×8 m) grid, with a minimum separation distance of 1m, was installed at each site to quantify the spatial variability of carbon exchange, soil moisture and temperature. Vegetation characteristics showed closer relation with soil development across the studied sites. ER reached 2.26μmolCO2m(-2)s(-1) in site 3, where ST was higher (7.53°C). A greater sink effect was revealed in site 4 (net uptake of 1.54μmolCO2m(-2)s(-1)) associated with higher SM (0.32m(3)m(-3)). Spherical models were fitted to describe all experimental semivariograms. Results indicate that ST and SM are directly related to the spatial variability of CO2 exchange. Heterogeneous vegetation patches showed smaller range values. Overall, poorly drained terrestrial ecosystems act as CO2 sink. Conversely, where ER is more pronounced, they are associated with intense soil carbon mineralization. The formations of new ice-free areas, depending on the local soil drainage condition, have an important effect on CO2 exchange. With increasing ice/snow melting, and resulting widespread waterlogging, increasing CO2 sink in terrestrial ecosystems is expected for Maritime Antarctica. Copyright © 2016 Elsevier B.V. All rights reserved.

UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation.

PubMed

Luo, Feng; Yan, Changsheng; Dang, Lilong; Krishna, Rajamani; Zhou, Wei; Wu, Hui; Dong, Xinglong; Han, Yu; Hu, Tong-Liang; O'Keeffe, Michael; Wang, Lingling; Luo, Mingbiao; Lin, Rui-Biao; Chen, Banglin

2016-05-04

A new metal-organic framework Zn2(H2O)(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the well-established MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn(2+) sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm(3)/cm(3)) to Zn-MOF-74. Interestingly, the accessible Zn(2+) sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm(3)/cm(3)) than Zn-MOF-74 (146 cm(3)/cm(3)) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result.

Fault Networks in the Northwestern Albuquerque Basin and Their Potential Role in Controlling Mantle CO2 Degassing and Fluid Migration from the Valles Caldera

NASA Astrophysics Data System (ADS)

Smith, J. R.; Crossey, L. J.; Karlstrom, K. E.; Fischer, T. P.; Lee, H.; McGibbon, C. J.

2015-12-01

The Rio Grande rift (RGR) has Quaternary and active volcanism and faulting that provide a field laboratory for examining links between mantle degassing and faults as fluid conduits. Diffuse and spring CO2 flux measurements were taken at 6 sites in the northwestern Albuquerque Basin (NWAB) and Valles caldera geothermal system. All sites progress to the southwest from the 1.25 Ma Valles caldera, down the rift-related Jemez fault network, to intersect with the Nacimiento fault system. Mantle CO2 and He degassing are well documented at 5 of 6 sites, with decreasing 3He/4He ratios away from the caldera. The instrument used to measure CO2 flux was an EGM-4 CO2 gas analyzer (PP systems) with an accumulation chamber. Carbonic springs at Penasco Springs (PS) and San Ysidro (SY), and the carbonate-cemented Sand Hill Fault (SHF) were targeted, all near the western border of the RGR. The SHF has no spring activity, had the smallest maximum flux of all the sites (8 g/m2d), but carbonate along the fault zone (<2 m wide) attest to past CO2 flux. The other two sites are equal distance (30-40 km) between the SHF site and Valles caldera sites. These sites have active carbonic springs that precipitate travertine mounds. Our work suggests these sites reflect intersections of the Nacimiento fault with NE trending faults that connect to the Jemez fault network. The maximum diffuse flux recorded at SY (297 g/m2d) and PS (25 g/m2d) are high, especially along the fault and near springs. At SY and PS the instruments capacity was exceeded (2,400 g/m2d) at 6 of 9 springs. Interpretations indicate a direct CO2 flux through a fault-related artesian aquifer system that is connected to magmatic gases from the caldera. Maximum diffuse flux measurements of Alamo Canyon (20,906 g/m2d), Sulphur Springs (2,400 g/m2d) and Soda Dam (1,882 g/m2d) at Valles caldera geothermal sites are comparable to Yellowstone geothermal systems. We use geospatial analysis and local geologic mapping to examine relationships of CO2 flux to structure. Travertine mounds can create impermeable barriers that modify near-surface degassing patterns, making it difficult to decipher where CO2 and fluids preferentially migrate up the damage zones in the hanging-wall or footwall. Future work will utilize grids to more accurately assess the localized affect fault zones have on CO2 flux rates.

Biofuel on contaminated land

NASA Astrophysics Data System (ADS)

Suer, Pascal; Andersson-Sköld, Yvonne; Blom, Sonja; Bardos, Paul; Polland, Marcel; Track, Thomas

2010-05-01

Desktop studies of two Swedish contaminated sites has indicated that growing biofuel crops on these sites may be more environmentally beneficial than alternative risk management approaches such as excavation / removal or containment The demand for biofuel increases pressure on the cultivatable soil of the world. While contaminated land is not very suitable for food production, cultivation of low and medium contaminated soil may remove some pressure from agricultural soils. For larger sites, biofuel cultivation may be economically viable without a remediation bonus. Suitable sites have topographic conditions that allow agricultural machinery, are not in urgent need of remediation, and contamination levels are not plant toxic. Life cycle assessment (LCA) was done for two cases. The (desk top) case studies were - Case K, a 5000 m2 site where salix (willow) was cultivated with hand-held machinery and the biofuel harvest was left on site, and - Case F, a 12 ha site were on site ensuring was being considered, and were salix might have rented an economic profit if the remediation had not been urgent due to exploitation pressure. Some selected results for biofuel K; biofuel F; excavation K; and on site ensuring F respectively: Energy: 0,05; 1,4; 3,5; 19 TJ Waste: 1; 9; 1200; 340 ton Land use off-site: 190; 3 500; 200 000; 1 400 000 m² a Global warming: 3; 86; 230; 1 200 ton CO2 eq Acidification: 25; 1 000; 2 600; 14 000 kg SO2 eq Photochemical smog: 10; 180; 410; 2 300 kg ethene eq Human health: 2; 51; 150; 620 index The environmental impact of the traditional remediation methods of excavation and on-site ensuring was mainly due to the transport of contaminated soil and replacement soil, and landfilling of the contaminated soil. Biofuel cultivation avoids these impacts, while fertiliser production and agricultural machinery would have a lower environmental impact than moving large volumes of soil around. Journeys of a controller to check on the groundwater quality also contributed to the biofuel impacts. The net CO2 equivalent emission on a 100 year basis per MJ energy in the Salix Vinimalis was between -0.02 and -0.1 kgCO2e/MJ. The fate of the stubble and roots of the salix was crucial for the carbon footprint. While stubble and roots remain in the soil (as increased soil organic matter), the carbon dioxide they took up while growing is not contributing to global warming. This pool was much larger than the CO2 emissions from soil transport and other processes. Biodiversity was difficult to include, and the results are uncertain. But the results indicated that biodiversity impact of biofuel cultivation may be large compared to "easier" categories like global warming and human health, and the net impact of biofuel cultivation may well be benifical to the environment instead of damaging.

Element mobilization and immobilization from carbonate rocks between CO2 storage reservoirs and the overlying aquifers during a potential CO2 leakage.

PubMed

Lawter, Amanda R; Qafoku, Nikolla P; Asmussen, R Matthew; Kukkadapu, Ravi K; Qafoku, Odeta; Bacon, Diana H; Brown, Christopher F

2018-04-01

Despite the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in this intermediate zone. After rocks reacted with CO 2 -acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2 -reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2 -laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

DOE PAGES

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew; ...

2018-01-04

In spite of the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in thismore » intermediate zone. Furthermore, after rocks reacted with CO 2-acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew

In spite of the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in thismore » intermediate zone. Furthermore, after rocks reacted with CO 2-acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less

Inversely Estimating the Vertical Profile of the Soil CO2 Production Rate in a Deciduous Broadleaf Forest Using a Particle Filtering Method

PubMed Central

Sakurai, Gen; Yonemura, Seiichiro; Kishimoto-Mo, Ayaka W.; Murayama, Shohei; Ohtsuka, Toshiyuki; Yokozawa, Masayuki

2015-01-01

Carbon dioxide (CO2) efflux from the soil surface, which is a major source of CO2 from terrestrial ecosystems, represents the total CO2 production at all soil depths. Although many studies have estimated the vertical profile of the CO2 production rate, one of the difficulties in estimating the vertical profile is measuring diffusion coefficients of CO2 at all soil depths in a nondestructive manner. In this study, we estimated the temporal variation in the vertical profile of the CO2 production rate using a data assimilation method, the particle filtering method, in which the diffusion coefficients of CO2 were simultaneously estimated. The CO2 concentrations at several soil depths and CO2 efflux from the soil surface (only during the snow-free period) were measured at two points in a broadleaf forest in Japan, and the data were assimilated into a simple model including a diffusion equation. We found that there were large variations in the pattern of the vertical profile of the CO2 production rate between experiment sites: the peak CO2 production rate was at soil depths around 10 cm during the snow-free period at one site, but the peak was at the soil surface at the other site. Using this method to estimate the CO2 production rate during snow-cover periods allowed us to estimate CO2 efflux during that period as well. We estimated that the CO2 efflux during the snow-cover period (about half the year) accounted for around 13% of the annual CO2 efflux at this site. Although the method proposed in this study does not ensure the validity of the estimated diffusion coefficients and CO2 production rates, the method enables us to more closely approach the “actual” values by decreasing the variance of the posterior distribution of the values. PMID:25793387

The Sulcis Storage Project: Status of the First Italian Initiative for Pilot-Scale Geological Sequestration of CO2

NASA Astrophysics Data System (ADS)

Plaisant, A.; Maggio, E.; Pettinau, A.

2016-12-01

The deep aquifer located at a depth of about 1000-1500 m within fractured carbonate in the Sulcis coal basin (South-West Sardinia, Italy) constitutes a potential reservoir to develop a pilot-scale CO2 storage site. The occurrence of several coal mines and the geology of the basin also provide favourable condition to install a permanent infrastructures where advanced CO2 storage technologies can be developed. Overall, the Sulcis project will allow to characterize the Sulcis coal basin (South West Sardinia, Italy) and to develop a permanent infrastructure (know-how, equipment, laboratories, etc.) for advanced international studies on CO2 storage. The research activities are structured in two different phases: (i) site characterization, including the construction of an underground and a fault laboratories and (ii) the installation of a test site for small-scale injection of CO2. In particular, the underground laboratory will host geochemical and geophysical experiments on rocks, taking advantages of the buried environment and the very well confined conditions in the galleries; in parallel, the fault laboratory will be constructed to study CO2 leakage phenomena in a selected fault. The project is currently ongoing and some preliminary results will be presented in this work as well as the structure of the project as a whole. More in detail, preliminary activities comprise: (i) geochemical monitoring; (ii) the minero-petrographycal, physical and geophysical characterization of the rock samples; (iii) the development of both static and dynamic geological models of the reservoir; (iv) the structural geology and fault analysis; (v) the assessment of natural seismicity through a monitoring network (vi) the re-processing and the analysis of the reflection seismic data. Future activities will comprise: (i) the drilling of shallow exploration wells near the faults; (ii) the construction of both the above mentioned laboratories; (iii) drilling of a deep exploration well (1,500 m); (iv) injection tests. Preliminary analyses show that the rocks of the carbonate formation present a low porosity, but the formation is characterized by a good permeability for fractures and karst. The faults are typically sealed and petrophysical properties of caprock and reservoir are spatially heterogeneous.

Quantifying the benefit of wellbore leakage potential estimates for prioritizing long-term MVA well sampling at a CO2 storage site.

PubMed

Azzolina, Nicholas A; Small, Mitchell J; Nakles, David V; Glazewski, Kyle A; Peck, Wesley D; Gorecki, Charles D; Bromhal, Grant S; Dilmore, Robert M

2015-01-20

This work uses probabilistic methods to simulate a hypothetical geologic CO2 storage site in a depleted oil and gas field, where the large number of legacy wells would make it cost-prohibitive to sample all wells for all measurements as part of the postinjection site care. Deep well leakage potential scores were assigned to the wells using a random subsample of 100 wells from a detailed study of 826 legacy wells that penetrate the basal Cambrian formation on the U.S. side of the U.S./Canadian border. Analytical solutions and Monte Carlo simulations were used to quantify the statistical power of selecting a leaking well. Power curves were developed as a function of (1) the number of leaking wells within the Area of Review; (2) the sampling design (random or judgmental, choosing first the wells with the highest deep leakage potential scores); (3) the number of wells included in the monitoring sampling plan; and (4) the relationship between a well’s leakage potential score and its relative probability of leakage. Cases where the deep well leakage potential scores are fully or partially informative of the relative leakage probability are compared to a noninformative base case in which leakage is equiprobable across all wells in the Area of Review. The results show that accurate prior knowledge about the probability of well leakage adds measurable value to the ability to detect a leaking well during the monitoring program, and that the loss in detection ability due to imperfect knowledge of the leakage probability can be quantified. This work underscores the importance of a data-driven, risk-based monitoring program that incorporates uncertainty quantification into long-term monitoring sampling plans at geologic CO2 storage sites.

Development of the Methodology Needed to Quantify Risks to Groundwater at CO2 Storage Sites

NASA Astrophysics Data System (ADS)

Brown, C. F.; Birkholzer, J. T.; Carroll, S.; Hakala, A.; Keating, E. H.; Lopano, C. L.; Newell, D. L.; Spycher, N.

2011-12-01

The National Risk Assessment Partnership (NRAP) is an effort that harnesses capabilities across five U.S. Department of Energy (DOE) national laboratories into a mission-focused platform to develop a defensible, science-based quantitative methodology for determining risk profiles at CO2 storage sites. NRAP is conducting risk and uncertainty analysis in the areas of reservoir performance, natural leakage pathways, wellbore integrity, groundwater protection, monitoring, and systems level modeling. The mission of NRAP is "to provide the scientific underpinning for risk assessment with respect to the long-term storage of CO2, including assessment of residual risk associated with a site post-closure." Additionally, NRAP will develop a strategic, risk-based monitoring protocol, such that monitoring at all stages of a project effectively minimizes uncertainty in the predicted behavior of the site, thereby increasing confidence in storage integrity. NRAP's research focus in the area of groundwater protection is divided into three main tasks: 1) development of quantitative risk profiles for potential groundwater impacts; 2) filling key science gaps in developing those risk profiles; and 3) field-based confirmation. Within these three tasks, researchers are engaged in collaborative studies to determine metrics to identify system perturbation and their associated risk factors. Reservoir simulations are being performed to understand/predict consequences of hypothetical leakage scenarios, from which reduced order models are being developed to feed risk profile development. Both laboratory-based experiments and reactive transport modeling studies provide estimates of geochemical impacts over a broad range of leakage scenarios. This presentation will provide an overview of the research objectives within NRAP's groundwater protection focus area, as well as select accomplishments achieved to date.

Effects of acute ocean acidification on spatially-diverse polar pelagic foodwebs: Insights from on-deck microcosms

NASA Astrophysics Data System (ADS)

Tarling, G. A.; Peck, V. L.; Ward, P.; Ensor, N. S.; Achterberg, E.; Tynan, E.; Poulton, A. J.; Mitchell, E.; Zubkov, M. V.

2016-05-01

The polar oceans are experiencing some of the largest levels of ocean acidification (OA) resulting from the uptake of anthropogenic carbon dioxide (CO2). Our understanding of the impacts this is having on polar marine communities is mainly derived from studies of single species in laboratory conditions, while the consequences for food web interactions remain largely unknown. This study carried out experimental manipulations of natural pelagic communities at different high latitude sites in both the northern (Nordic Seas) and southern hemispheres (Scotia and Weddell Seas). The aim of this study was to identify more generic responses and achieve greater experimental reproducibility through implementing a series of short term (4 d), multilevel (3 treatment) carbonate chemistry manipulation experiments on unfiltered natural surface-ocean communities, including grazing copepods. The experiments were successfully executed at six different sites, covering a diverse range of environmental conditions and differing plankton community compositions. The study identified the interaction between copepods and dinoflagellate cell abundance to be significantly altered by elevated levels of dissolved CO2 (pCO2), with dinoflagellates decreasing relative to ambient conditions across all six experiments. A similar pattern was not observed in any other major phytoplankton group. The patterns indicate that copepods show a stronger preference for dinoflagellates when in elevated pCO2 conditions, demonstrating that changes in food quality and altered grazing selectivity may be a major consequence of ocean acidification. The study also found that transparent exopolymeric particles (TEP) generally increased when pCO2 levels were elevated, but the response was dependent on the exact set of environmental conditions. Bacteria and nannoplankton showed a neutral response to elevated pCO2 and there was no significant relationship between changes in bacterial or nannoplankton abundance and that of TEP concentrations. Overall, the study illustrated that, although some similar responses exist, these contrasting high latitude surface ocean communities are likely to show different responses to the onset of elevated pCO2.

Natural analogue study of CO2 storage monitoring using probability statistics of CO2-rich groundwater chemistry

NASA Astrophysics Data System (ADS)

Kim, K. K.; Hamm, S. Y.; Kim, S. O.; Yun, S. T.

2016-12-01

For confronting global climate change, carbon capture and storage (CCS) is one of several very useful strategies as using capture of greenhouse gases like CO2 spewed from stacks and then isolation of the gases in underground geologic storage. CO2-rich groundwater could be produced by CO2 dissolution into fresh groundwater around a CO2 storage site. As consequence, natural analogue studies related to geologic storage provide insights into future geologic CO2 storage sites as well as can provide crucial information on the safety and security of geologic sequestration, the long-term impact of CO2 storage on the environment, and field operation and monitoring that could be implemented for geologic sequestration. In this study, we developed CO2 leakage monitoring method using probability density function (PDF) by characterizing naturally occurring CO2-rich groundwater. For the study, we used existing data of CO2-rich groundwaters in different geological regions (Gangwondo, Gyeongsangdo, and Choongchungdo provinces) in South Korea. Using PDF method and QI (quantitative index), we executed qualitative and quantitative comparisons among local areas and chemical constituents. Geochemical properties of groundwater with/without CO2 as the PDF forms proved that pH, EC, TDS, HCO3-, Ca2+, Mg2+, and SiO2 were effective monitoring parameters for carbonated groundwater in the case of CO2leakage from an underground storage site. KEY WORDS: CO2-rich groundwater, CO2 storage site, monitoring parameter, natural analogue, probability density function (PDF), QI_quantitative index Acknowledgement This study was supported by the "Basic Science Research Program through the National Research Foundation of Korea (NRF), which is funded by the Ministry of Education (NRF-2013R1A1A2058186)" and the "R&D Project on Environmental Management of Geologic CO2 Storage" from KEITI (Project number: 2014001810003).

Molecular simulations for adsorption and separation of natural gas in IRMOF-1 and Cu-BTC metal-organic frameworks.

PubMed

Martín-Calvo, Ana; García-Pérez, Elena; Manuel Castillo, Juan; Calero, Sofia

2008-12-21

We use Monte Carlo simulations to study the adsorption and separation of the natural gas components in IRMOF-1 and Cu-BTC metal-organic frameworks. We computed the adsorption isotherms of pure components, binary, and five-component mixtures analyzing the siting of the molecules in the structure for the different loadings. The bulk compositions studied for the mixtures were 50 : 50 and 90 : 10 for CH4-CO2, 90 : 10 for N2-CO2, and 95 : 2.0 : 1.5 : 1.0 : 0.5 for the CH4-C2H6-N2-CO2-C3H8 mixture. We choose this composition because it is similar to an average sample of natural gas. Our simulations show that CO2 is preferentially adsorbed over propane, ethane, methane and N2 in the complete pressure range under study. Longer alkanes are favored over shorter alkanes and the lowest adsorption corresponds to N2. Though IRMOF-1 has a significantly higher adsorption capacity than Cu-BTC, the adsorption selectivity of CO2 over CH4 and N2 is found to be higher in the latter, proving that the separation efficiency is largely affected by the shape, the atomic composition and the type of linkers of the structure.

El Niño Southern Oscillation (ENSO) Enhances CO2 Exchange Rates in Freshwater Marsh Ecosystems in the Florida Everglades

PubMed Central

Malone, Sparkle L.; Staudhammer, Christina L.; Oberbauer, Steven F.; Olivas, Paulo; Ryan, Michael G.; Schedlbauer, Jessica L.; Loescher, Henry W.; Starr, Gregory

2014-01-01

This research examines the relationships between El Niño Southern Oscillation (ENSO), water level, precipitation patterns and carbon dioxide (CO2) exchange rates in the freshwater wetland ecosystems of the Florida Everglades. Data was obtained over a 5-year study period (2009–2013) from two freshwater marsh sites located in Everglades National Park that differ in hydrology. At the short-hydroperiod site (Taylor Slough; TS) and the long-hydroperiod site (Shark River Slough; SRS) fluctuations in precipitation patterns occurred with changes in ENSO phase, suggesting that extreme ENSO phases alter Everglades hydrology which is known to have a substantial influence on ecosystem carbon dynamics. Variations in both ENSO phase and annual net CO2 exchange rates co-occurred with changes in wet and dry season length and intensity. Combined with site-specific seasonality in CO2 exchanges rates, El Niño and La Niña phases magnified season intensity and CO2 exchange rates at both sites. At TS, net CO2 uptake rates were higher in the dry season, whereas SRS had greater rates of carbon sequestration during the wet season. As La Niña phases were concurrent with drought years and extended dry seasons, TS became a greater sink for CO2 on an annual basis (−11 to −110 g CO2 m−2 yr−1) compared to El Niño and neutral years (−5 to −43.5 g CO2 m−2 yr−1). SRS was a small source for CO2 annually (1.81 to 80 g CO2 m−2 yr−1) except in one exceptionally wet year that was associated with an El Niño phase (−16 g CO2 m−2 yr−1). Considering that future climate predictions suggest a higher frequency and intensity in El Niño and La Niña phases, these results indicate that changes in extreme ENSO phases will significantly alter CO2 dynamics in the Florida Everglades. PMID:25521299

CO2 dispersion modelling over Paris region within the CO2-MEGAPARIS project

NASA Astrophysics Data System (ADS)

Lac, C.; Donnelly, R. P.; Masson, V.; Pal, S.; Donier, S.; Queguiner, S.; Tanguy, G.; Ammoura, L.; Xueref-Remy, I.

2012-10-01

Accurate simulation of the spatial and temporal variability of tracer mixing ratios over urban areas is challenging, but essential in order to utilize CO2 measurements in an atmospheric inverse framework to better estimate regional CO2 fluxes. This study investigates the ability of a high-resolution model to simulate meteorological and CO2 fields around Paris agglomeration, during the March field campaign of the CO2-MEGAPARIS project. The mesoscale atmospheric model Meso-NH, running at 2 km horizontal resolution, is coupled with the Town-Energy Balance (TEB) urban canopy scheme and with the Interactions between Soil, Biosphere and Atmosphere CO2-reactive (ISBA-A-gs) surface scheme, allowing a full interaction of CO2 between the surface and the atmosphere. Statistical scores show a good representation of the Urban Heat Island (UHI) and urban-rural contrasts. Boundary layer heights (BLH) at urban, sub-urban and rural sites are well captured, especially the onset time of the BLH increase and its growth rate in the morning, that are essential for tall tower CO2 observatories. Only nocturnal BLH at sub-urban sites are slightly underestimated a few nights, with a bias less than 50 m. At Eiffel tower, the observed spikes of CO2 maxima occur every morning exactly at the time at which the Atmospheric Boundary Layer (ABL) growth reaches the measurement height. The timing of the CO2 cycle is well captured by the model, with only small biases on CO2 concentrations, mainly linked to the misrepresentation of anthropogenic emissions, as the Eiffel site is at the heart of trafic emission sources. At sub-urban ground stations, CO2 measurements exhibit maxima at the beginning and at the end of each night, when the ABL is fully contracted, with a very strong spatio-temporal variability. The CO2 cycle at these sites is generally well reproduced by the model, even if some biases on the nocturnal maxima appear in the Paris plume parly due to small errors on the vertical transport, or in the vicinity of airports due to small errors on the horizontal transport (wind direction). A sensitivity test without urban parameterisation removes UHI and underpredicts nighttime BLH over urban and sub-urban sites, leading to large overestimation of nocturnal CO2 concentration at the sub-urban sites. The agreement of daytime and nighttime BLH and CO2 predictions of the reference simulation over Paris agglomeration demonstrates the potential of using the meso-scale system on urban and sub-urban area in the context of inverse modelling.

Effect of Co and O defects on ferromagnetism in Co-doped ZnO: An X-ray absorption spectroscopic investigation

NASA Astrophysics Data System (ADS)

Singhal, Rishi K.; Jakhar, Narendra; Samariya, A.; Dolia, S. N.; Kumar, Sudhish

2018-02-01

Understanding of origin of ferromagnetism in dilute magnetic oxides (DMO's) has become one of the most challenging research problems in condensed matter physics. Here we are reporting a detailed study of magnetic properties and electronic structure of two 5% Co-doped ZnO samples (the as-prepared sample Zn0.95Co0.05O and the hydrogenated sample Zn0.95Co0.05O:H). The as-prepared sample is found to be paramagnetic while through hydrogenation, we observed inducement of remarkable ferromagnetism in it. The H-mediated magnetic transition is accompanied by electronic structure modifications with no structural deviations. To get in-depth information into electronic structure correlations of the observed ferromagnetism, we have investigated their electronic properties in detail. For this purpose, we have employed the site-selective and element-sensitive X-ray-absorption spectroscopy (XAS) in the vicinity of the Cobalt L2,3 edge, the oxygen K edge, and the Zinc L3 edge using synchrotron radiation. The Co L2,3 edge spectra clearly show that Co dopants reside at the Zn sites for both these samples and that they are tetrahedrally coordinated with the ligand O atoms. Very minor changes are observed in the Zn L3 edge spectra. However, the O 1s edge spectra display dominant additional components in the ferromagnetic hydrogenated sample Zn0.95Co0.05O:H, not observed in the as-prepared non-magnetic sample Zn0.95Co0.05O. We conclude that the observed spectral features can be attributed to the presence of O vacancies and the hybridization of Co 3d states with O 2p vacancy states. These two factors together are likely to play important role in inducement of ferromagnetic ordering in this Co-doped ZnO system. However, which of these two weighs more in this mechanism, cannot be pinpointed and more studies are required in this regard.

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2,6-(mesityl)2} and reversible CO addition at the Ni site

PubMed Central

Ohki, Yasuhiro; Yasumura, Kazunari; Ando, Masaru; Shimokata, Satoko; Tatsumi, Kazuyuki

2010-01-01

A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)3Fe(μ-StBu)3Ni(SDmp), 1 (Dmp = C6H3-2,6-(mesityl)2), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex [(CO)3Fe(μ-StBu)3Ni]2(μ-Br)2, 2 with NaSDmp at -40 °C. The nickel site of complex 1 was found to add CO or CNtBu at -40 °C to give (CO)3Fe(StBu)(μ-StBu)2Ni(CO)(SDmp), 3, or (CO)3Fe(StBu)(μ-StBu)2Ni(CNtBu)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055 cm-1 in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CNtBu adduct 4 is more robust. PMID:20147622

Interfacial Engineering of Hierarchical Transition Metal Oxide Heterostructures for Highly Sensitive Sensing of Hydrogen Peroxide.

PubMed

Zhang, Wen; Fan, Guozheng; Yi, Huan; Jia, Gan; Li, Zhaosheng; Yuan, Chunwei; Bai, Yunfei; Fu, Degang

2018-05-01

Hydrogen peroxide (H 2 O 2 ) is a major messenger molecule in cellular signal transduction. Direct detection of H 2 O 2 in complex environments provides the capability to illuminate its various biological functions. With this in mind, a novel electrochemical approach is here proposed by integrating a series of CoO nanostructures on CuO backbone at electrode interfaces. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction, and X-ray photoelectron spectroscopy demonstrate successful formation of core-shell CuO-CoO hetero-nanostructures. Theoretical calculations further confirm energy-favorable adsorption of H 2 O 2 on surface sites of CuO-CoO heterostructures. Contributing to the efficient electron transfer path and enhanced capture of H 2 O 2 in the unique leaf-like CuO-CoO hierarchical 3D interface, an optimal biosensor-based CuO-CoO-2.5 h electrode exhibits an ultrahigh sensitivity (6349 µA m m -1 cm -2 ), excellent selectivity, and a wide detection range for H 2 O 2 , and is capable of monitoring endogenous H 2 O 2 derived from human lung carcinoma cells A549. The synergistic effects for enhanced H 2 O 2 adsorption in integrated CuO-CoO nanostructures and performance of the sensor suggest a potential for exploring pathological and physiological roles of reactive oxygen species like H 2 O 2 in biological systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 and CO emission rates from three forest fire controlled experiments in Western Amazonia

NASA Astrophysics Data System (ADS)

Carvalho, J. A., Jr.; Amaral, S. S.; Costa, M. A. M.; Soares Neto, T. G.; Veras, C. A. G.; Costa, F. S.; van Leeuwen, T. T.; Krieger Filho, G. C.; Tourigny, E.; Forti, M. C.; Fostier, A. H.; Siqueira, M. B.; Santos, J. C.; Lima, B. A.; Cascão, P.; Ortega, G.; Frade, E. F., Jr.

2016-06-01

Forests represent an important role in the control of atmospheric emissions through carbon capture. However, in forest fires, the carbon stored during photosynthesis is released into the atmosphere. The carbon quantification, in forest burning, is important for the development of measures for its control. The aim of this study was to quantify CO2 and CO emissions of forest fires in Western Amazonia. In this paper, results are described of forest fire experiments conducted in Cruzeiro do Sul and Rio Branco, state of Acre, and Candeias do Jamari, state of Rondônia, Brazil. These cities are located in the Western portion of the Brazilian Amazon region. The biomass content per hectare, in the virgin forest, was measured by indirect methods using formulas with parameters of forest inventories in the central hectare of the test site. The combustion completeness was estimated by randomly selecting 10% of the total logs and twelve 2 × 2 m2 areas along three transects and examining their consumption rates by the fire. The logs were used to determine the combustion completeness of the larger materials (characteristic diameters larger than 10 cm) and the 2 × 2 m2 areas to determine the combustion completeness of small-size materials (those with characteristic diameters lower than 10 cm) and the. The overall biomass consumption by fire was estimated to be 40.0%, 41.2% and 26.2%, in Cruzeiro do Sul, Rio Branco and Candeias do Jamari, respectively. Considering that the combustion gases of carbon in open fires contain approximately 90.0% of CO2 and 10.0% of CO in volumetric basis, the average emission rates of these gases by the burning process, in the three sites, were estimated as 191 ± 46.7 t ha-1 and 13.5 ± 3.3 t ha-1, respectively.

Sorption of Sr, Co and Zn on illite: Batch experiments and modelling including Co in-diffusion measurements on compacted samples

NASA Astrophysics Data System (ADS)

Montoya, V.; Baeyens, B.; Glaus, M. A.; Kupcik, T.; Marques Fernandes, M.; Van Laer, L.; Bruggeman, C.; Maes, N.; Schäfer, T.

2018-02-01

Experimental investigations on the uptake of divalent cations (Sr, Co and Zn) onto illite (Illite du Puy, Le-Puy-en-Velay, France) were carried out by three different international research groups (Institute for Nuclear Waste Disposal, KIT (Germany), Group Waste & Disposal, SCK-CEN, (Belgium) and Laboratory for Waste Management, PSI (Switzerland)) in the framework of the European FP7 CatClay project. The dependence of solid-liquid distribution ratios (Rd values) on pH at trace metal conditions (sorption edges) and on the metal ion concentration (sorption isotherms) was determined in dilute suspensions of homo-ionic Na-illite (Na-IdP) under controlled N2 atmosphere. The experimental results were modelled using the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model. The sorption of Sr depends strongly on ionic strength, while a rather weak pH dependence is observed in a pH range between 3 and 11. The data were modelled with cation exchange reactions, taking into account competition with H, K, Ca, Mg and Al, and surface complexation on weak amphotheric edge sites at higher pH values. The sorption of Co on Na-IdP, however, is strongly pH dependent. Cation exchange on the planar sites and surface complexation on strong and weak amphoteric edge sites were used to describe the Co sorption data. Rd values for Co derived from in-diffusion measurements on compacted Na-IdP samples (bulk-dry density of 1700 kg m-3) between pH 5.0 and 9.0 are in good agreement with the batch sorption data. The equivalence of both approaches to measure sorption was thus confirmed for the present test system. In addition, the results highlight the importance of both major and minor surface species for the diffusive transport behaviour of strongly sorbing metal cations. While surface complexes at the edge sites determine largely the Rd value, the diffusive flux may be governed by those species bound to the planar sites, even at low fractional occupancies. The pH dependent sorption determined for trace Zn concentrations showed large Rd values across the entire pH range with almost no dependence on the background electrolyte concentration. Additional sorption experiments carried out at substantial fractional Zn loadings demonstrated that the selectivity for the exchange of Na+ for Zn2+ at the planar sites could not explain the large Rd values measured at low pH and trace Zn concentrations. This suggests that another mechanism is ruling Zn uptake under these conditions.

Increased CO2 selectivity of asphalt-derived porous carbon through introduction of water into pore space

NASA Astrophysics Data System (ADS)

Jalilov, Almaz S.; Li, Yilun; Kittrell, Carter; Tour, James M.

2017-12-01

The development of inexpensive porous solid sorbents, such as porous carbons, that can selectively capture carbon dioxide (CO2) from natural gas wells is essential to reduce emission of CO2 to the atmosphere. However, at higher pressures, the selectivity for CO2 over that for methane (CH4) remains poor. Here we show that H2O can be imbibed within asphalt-derived porous carbon, with a surface area of 4,200 m2 g-1, to generate a hydrated powder material. While maintaining a high CO2 uptake capacity of 48 mmol g-1 (211 wt%), the molar selectivity for CO2 over CH4 increases to >200:1 and the H2O remains within the pores on repeated cycling. To mimic realistic natural gas wells, we used a 90% CH4 and 10% CO2 gas mixture and showed selective CO2 separation at 20 bar. Furthermore, in situ vibrational spectroscopy reveals the formation of an ordered matrix within the pores consisting of gas hydrates.

Sources and sinks of selected trace gases in the tropospheric boundary layer of the eastern United States

NASA Astrophysics Data System (ADS)

White, Marguerite L.

This dissertation describes three major research projects with the common goal of characterizing sources and sinks of trace gases of strong relevance to regional air quality and global climate issues. In the first study, volatile organic compound (VOC) measurements collected at a marine and continental site in northern New England were compared and examined for evidence of regional VOC sources. Biogenic VOCs, including isoprene, monoterpenes, and oxygenated VOCs, were significant components of the total reactivity at both locations. However, very different VOC distributions were observed for each site. The impact of local anthropogenic hydrocarbon sources such as liquefied petroleum gas (LPG) leakage was also evident at both sites. During the campaign, a propane flux of 9 (+/-2) x 109 molecules cm-2 s-1 was calculated for the continental site. In the second study, three hydrocarbon sources were investigated for their potential contributions to the summertime atmospheric toluene enhancements observed at a rural location in southern New Hampshire. These sources included: (1) warm season fuel evaporation emissions, (2) local industrial emissions, and (3) local vegetative emissions. The estimated contribution of fuel evaporation emissions (16-30 pptv d-1) could not fully account for observed summertime toluene enhancements (20-50 pptv d-1). Vegetation enclosure measurements suggested biogenic toluene emissions (5 and 12 pptv d-1 for alfalfa and pine trees) made significant contributions to summertime enhancements. Industrial toluene emissions, estimated at 7 pptv d-1, most likely occurred year round rather than seasonally. Finally, controls over carbonyl sulfide (COS) uptake in a temperate loblolly pine forest grown under ambient and elevated CO2 were examined in the third study. Vegetative consumption dominated net ecosystem COS uptake (10 to 40 pmol m-2 s-1) under both CO2 regimes. Environmental controls over vegetation stomatal conductance and photosynthetic capacity were the major factors influencing COS uptake rates. The loblolly pines exhibited substantial COS consumption overnight (50% of daytime rates) that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated.

CO dissociation and CO hydrogenation on smooth and ion-bombarded Pd(1 1 1): SFG and XPS spectroscopy at mbar pressures

NASA Astrophysics Data System (ADS)

Rupprechter, G.; Kaichev, V. V.; Unterhalt, H.; Morkel, M.; Bukhtiyarov, V. I.

2004-07-01

The CO dissociation probability on transition metals is often invoked to explain the product distribution (selectivity) of catalytic CO hydrogenation. Along these lines, we have investigated CO adsorption and dissociation on smooth and ion-bombarded Pd(1 1 1) at pressures up to 1 mbar using vibrational sum frequency generation (SFG) and X-ray photoelectron spectroscopy (XPS). Under high pressure, CO adsorbate structures were observed that were identical to high-coverage structures in UHV. On ion-bombarded surfaces an additional species was detected which was attributed to CO bridge bonded to defect (low-coordinated) sites. On both surfaces, no indications of CO dissociation were found even after hours of 0.1 mbar CO exposure. However, exposing CO/H 2 mixtures to ion-bombarded Pd(1 1 1) produced carbonaceous deposits suggesting CH xO species as precursors for CO bond cleavage and that the formation of CH xO is facilitated by surface defects. The relevance of the observations for CO hydrogenation on Pd catalysts is discussed.

The alkenone method for pCO2 reconstructions: challenges and strategies

NASA Astrophysics Data System (ADS)

Zhang, Y.; Pearson, A.; Benthien, A.; Dong, L.; Henderiks, J.; Huybers, P. J.

2016-12-01

The alkenone-pCO2 method is one of the most widely used approaches to reconstruct atmospheric CO2 in the Cenozoic. The method depends upon fractionation of stable carbon isotopes, expressed as ɛp37:2, and a physiological scaling parameter, b, that accounts for algal growth rate and cell size. Alkenone-derived CO2 records for the late Pleistocene, however, often are poorly correlated with ice core CO2 records. We show that poor correlation largely results from (1) systematic overestimation of b and (2) low sensitivity of ɛp37:2 to atmospheric CO2 variations at low-productivity sites [1]. Records are presented from two sites with high ɛp37:2 sensitivity: the South China Sea (SCS) and the tropical Altantic Ocean. Values of b are back calculated to determine their full range over glacial-interglacial cycles using ɛp37:2, ice core pCO2 records, and ocean temperature reconstructions. Air-sea equilibrium of CO2 is assumed at both sites, and the high-resolution temperature record from the SCS site is tuned to ice core pCO2 to eliminate age model discrepancies. The mean value of b is applied to obtain pCO2 estimates. By definition, this approach must yield the correct mean value for pCO2, but observed amplitudes are also reproduced. We further explore the relationship between coccolithophore cell size and growth rate using coccolith size measurements and back-calculated values of b, which suggests a potential proxy to constrain the history of phytoplankton growth rate and b. [1] Zhang, Y.G., Pearson, A., Huybers, P. and Pagani, M, 2016, Refining the alkenone-pCO2 method: The role of algal growth conditions, Paleoceanography, in review

Selectivity of adsorption of gases on doped graphene

NASA Astrophysics Data System (ADS)

Nnabugwu, Jordan; Maiga, Sidi; Gatica, Silvina

We report our results on the selectivity of carbon dioxide being adsorbed onto doped graphene. Using the Ideal Adsorption Solution theory (IAST) we calculate the selectivity using the uptake pressures of pure gases. We focus on the adsorption of atmospheric gases such as carbon dioxide (CO2) , Nitrogen (N2) , and Methane (CH4) on a pure and doped monolayer graphene slab placed at the bottom of a simulation cell. Grand Canonical Monte Carlo (GCMC) simulations allow us to calculate the amount of gases adsorbed at a given temperature and pressure of the system. We found that including impurities of varying strength and concentration can increase significantly the selectivity at room temperature. Financial support from the National Science Foundation Research Experiences for Undergraduates Program for the REU Site in Physics at Howard University (NSF Award No. PHY-1358727) is gratefully acknowledged.

Nanowire-Assembled Hierarchical ZnCo2O4 Microstructure Integrated with a Low-Power Microheater for Highly Sensitive Formaldehyde Detection.

PubMed

Long, Hu; Harley-Trochimczyk, Anna; Cheng, Siyi; Hu, Hao; Chi, Won Seok; Rao, Ameya; Carraro, Carlo; Shi, Tielin; Tang, Zirong; Maboudian, Roya

2016-11-23

Nanowire-assembled 3D hierarchical ZnCo 2 O 4 microstructure is synthesized by a facile hydrothermal route and a subsequent annealing process. In comparison to simple nanowires, the resulting dandelion-like structure yields more open spaces between nanowires, which allow for better gas diffusion and provide more active sites for gas adsorption while maintaining good electrical conductivity. The hierarchical ZnCo 2 O 4 microstructure is integrated on a low-power microheater platform without using binders or conductive additives. The hierarchical structure of the ZnCo 2 O 4 sensing material provides reliable electrical connection across the sensing electrodes. The resulting sensor exhibits an ultralow detection limit of 3 ppb toward formaldehyde with fast response and recovery as well as good selectivity to CO, H 2 , and hydrocarbons such as n-pentane, propane, and CH 4 . The sensor only consumes ∼5.7 mW for continuous operation at 300 °C with good long-term stability. The excellent sensing performance of this hierarchical structure based sensor suggests the advantages of combining such structures with microfabricated heaters for practical low-power sensing applications.

Hydrogeological characterization of shallow-depth zone for CO2 injection and leak test at a CO2 environmental monitoring site in Korea

NASA Astrophysics Data System (ADS)

Lee, S. S.; Kim, T. W.; Kim, H. H.; Ha, S. W.; Jeon, W. T.; Lee, K. K.

2015-12-01

The main goal of the this study is to evaluate the importance of heterogeneities in controlling the field-scale transport of CO2 are originated from the CO2 injected at saturated zone below the water table for monitoring and prediction of CO2 leakage from a reservoir. Hydrogeological and geophysical data are collected to characterize the site, prior to conducting CO2 injection experiment at the CO2 environmental monitoring site at Eumseong, Korea. The geophysical data were acquired from borehole electromagnetic flowmeter tests, while the hydraulic data were obtained from pumping tests, slug tests, and falling head permeability tests. Total of 13 wells to perform hydraulic and geophysical test are established along groundwater flow direction in regular sequence, revealed by the results of borehole electromagnetic flowmeter test. The results of geophysical tests indicated that hydraulic gradient is not identical with the topographic gradient. Groundwater flows toward the uphill direction in the study area. Then, the hydraulic tests were conducted to identify the hydraulic properties of the study site. According to the results of pumping and slug tests at the study site, the hydraulic conductivity values show ranges between 4.75 x 10-5 cm/day and 9.74 x 10-5 cm/day. In addition, a portable multi-level sampling and monitoring packer device which remains inflated condition for a long period developed and used to isolate designated depths to identify vertical distribution of hydrogeological characteristics. Hydrogeological information obtained from this study will be used to decide the injection test interval of CO2-infused water and gaseous CO2. Acknowledgement: Financial support was provided by "R&D Project on Environmental Mangement of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).

Strain selection, biomass to biofuel conversion, and resource colocation have strong impacts on the economic performance of algae cultivation sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venteris, Erik R.; Wigmosta, Mark S.; Coleman, Andre M.

Decisions involving strain selection, biomass to biofuel technology, and the location of cultivation facilities can strongly influence the economic viability of an algae-based biofuel enterprise. In this contribution we summarize our past results in a new analysis to explore the relative economic impact of these design choices. We present strain-specific growth model results from two saline strains (Nannocloropsis salina, Arthrospira sp.), a fresh to brackish strain (Chlorella sp., DOE strain 1412), and a freshwater strain of the order Sphaeropleales. Biomass to biofuel conversion is compared between lipid extraction (LE) and hydrothermal liquefaction (HTL) technologies. National-scale models of water, CO2 (asmore » flue gas), land acquisition, site leveling, construction of connecting roads, and transport of HTL oil to existing refineries are used in conjunction with estimates of fuel value (from HTL) to prioritize and select from 88,692 unit farms (UF, 405 ha in pond area), a number sufficient to produce 136E+9 L yr-1 of renewable diesel (36 billion gallons yr-1, BGY). Strain selection and choice of conversion technology have large economic impacts, with differences between combinations of strains and biomass to biofuel technologies being up to $10 million dollars yr-1 UF-1. Results based on the most productive species, HTL-based fuel conversion, and resource costs show that the economic potential between geographic locations within the selection can differ by up to $4 million yr-1 UF-1, with 2.0 BGY of production possible from the most cost-effective sites. The local spatial variability in site rank is extreme, with very high and low rank sites within 10s of km of each other. Colocation with flue gas sources has a strong influence on site rank, but the most costly resource component varies from site to site. The highest rank sites are located predominantly in Florida and Texas, but most states south of 37°N latitude contain promising locations. Keywords: algae, biofuels, resource assessment, geographic information systems, techno-economics« less

CO2 geosequestration at the laboratory scale: Combined geophysical and hydromechanical assessment of weakly-cemented shallow Sleipner-like reservoirs

NASA Astrophysics Data System (ADS)

Falcon-Suarez, I.; North, L. J.; Best, A. I.

2017-12-01

To date, the most promising mitigation strategy for reducing global carbon emissions is Carbon Capture and Storage (CCS). The storage technology (i.e., CO2 geosequestration, CGS) consists of injecting CO2 into deep geological formations, specifically selected for such massive-scale storage. To guarantee the mechanical stability of the reservoir during and after injection, it is crucial to improve existing monitoring techniques for controlling CGS activities. We developed a comprehensive experimental program to investigate the integrity of the Sleipner CO2 storage site in the North Sea - the first commercial CCS project in history where 1 Mtn/y of CO2 has been injected since 1996. We assessed hydro-mechanical effects and the related geophysical signatures of three synthetic sandstones and samples from the Utsira Sand formation (main reservoir at Sleipner), at realistic pressure-temperature (PT) conditions and fluid compositions. Our experimental approach consists of brine-CO2 flow-through tests simulating variable inflation/depletion scenarios, performed in the CGS-rig (Fig. 1; Falcon-Suarez et al., 2017) at the National Oceanography Centre (NOC) in Southampton. The rig is designed for simultaneous monitoring of ultrasonic P- and S-wave velocities and attenuations, electrical resistivity, axial and radial strains, pore pressure and flow, during the co-injection of up to two fluids under controlled PT conditions. Our results show velocity-resistivity and seismic-geomechanical relations of practical importance for the distinction between pore pressure and pore fluid distribution during CGS activities. By combining geophysical and thermo-hydro-mechano-chemical coupled information, we can provide laboratory datasets that complement in situ seismic, geomechanical and electrical survey information, useful for the CO2 plume monitoring in Sleipner site and other shallow weakly-cemented sand CCS reservoirs. Falcon-Suarez, I., Marín-Moreno, H., Browning, F., Lichtschlag, A., Robert, K., North, L.J., Best, A.I., 2017. Experimental assessment of pore fluid distribution and geomechanical changes in saline sandstone reservoirs during and after CO2 injection. International Journal of Greenhouse Gas Control 63, 356-369.

Early opportunities of CO2 geological storage deployment in coal chemical industry in China

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Ning; Li, Xiaochun; Liu, Shengnan

2014-11-12

Abstract: Carbon dioxide capture and geological storage (CCS) is regarded as a promising option for climate change mitigation; however, the high capture cost is the major barrier to large-scale deployment of CCS technologies. High-purity CO2 emission sources can reduce or even avoid the capture requirements and costs. Among these high-purity CO2 sources, certain coal chemical industry processes are very important, especially in China. In this paper, the basic characteristics of coal chemical industries in China is investigated and analyzed. As of 2013 there were more than 100 coal chemical plants in operation or in late planning stages. These emission sourcesmore » together emit 430 million tons CO2 per year, of which about 30% are emit high-purity and pure CO2 (CO2 concentration >80% and >99% respectively).Four typical source-sink pairs are studied by a techno-economic evaluation, including site screening and selection, source-sink matching, concept design, and experienced economic evaluation. The technical-economic evaluation shows that the levelized cost of a CO2 capture and aquifer storage project in the coal chemistry industry ranges from 14 USD/t to 17 USD/t CO2. When a 15USD/t CO2 tax and 15USD/t for CO2 sold to EOR are considered, the levelized cost of CCS project are negative, which suggests a net economic benefit from some of these CCS projects. This might provide China early opportunities to deploy and scale-up CCS projects in the near future.« less

Evolution of CAM and C4 carbon-concentrating mechanisms

USGS Publications Warehouse

Keeley, Jon E.; Rundel, Philip W.

2003-01-01

Mechanisms for concentrating carbon around the Rubisco enzyme, which drives the carbon-reducing steps in photosynthesis, are widespread in plants; in vascular plants they are known as crassulacean acid metabolism (CAM) and C4 photosynthesis. CAM is common in desert succulents, tropical epiphytes, and aquatic plants and is characterized by nighttime fixation of CO2. The proximal selective factor driving the evolution of this CO2-concentrating pathway is low daytime CO2, which results from the unusual reverse stomatal behavior of terrestrial CAM species or from patterns of ambient CO2 availability for aquatic CAM species. In terrestrials the ultimate selective factor is water stress that has selected for increased water use efficiency. In aquatics the ultimate selective factor is diel fluctuations in CO2 availability for palustrine species and extreme oligotrophic conditions for lacustrine species. C4 photosynthesis is based on similar biochemistry but carboxylation steps are spatially separated in the leaf rather than temporally as in CAM. This biochemical pathway is most commonly associated with a specialized leaf anatomy known as Kranz anatomy; however, there are exceptions. The ultimate selective factor driving the evolution of this pathway is excessively high photorespiration that inhibits normal C3 photosynthesis under high light and high temperature in both terrestrial and aquatic habitats. CAM is an ancient pathway that likely has been present since the Paleozoic era in aquatic species from shallow-water palustrine habitats. While atmospheric CO2 levels have undoubtedly affected the evolution of terrestrial plant carbon-concentrating mechanisms, there is reason to believe that past atmospheric changes have not played as important a selective role in the aquatic milieu since palustrine habitats today are not generally carbon sinks, and the selective factors driving aquatic CAM are autogenic. Terrestrial CAM, in contrast, is of increasing selective value under extreme water deficits, and undoubtedly, high Mesozoic CO2 levels reduced the amount of landscape perceived by plants as water limited. Late Tertiary and Quaternary reductions in atmospheric CO2, coupled with increasing seasonality, were probably times of substantial species radiation and ecological expansion for CAM plants. C4 photosynthesis occurs in only about half as many families as CAM, and three-fourths of C4 species are either grasses or sedges. Molecular phylogenies indicate C4 is a more recent innovation than CAM and that it originated in the mid-Tertiary, 20–30 Ma, although some data support an earlier origin. While the timing of the origin of C4 remains controversial, the nearly explosive increase in C4 species is clearly documented in the late Miocene, 4–7 Ma. Increasing seasonality has been widely suggested as an important climatic stimulus for this C4 expansion. Alternatively, based on models of photosynthetic quantum yield at different temperatures and CO2 concentration, it has been hypothesized that the late Miocene C4 expansion resulted from declining atmospheric CO2 levels. This model is most appropriate for explaining the transition from C3 grasslands to C4 grasslands but by itself may not be sufficient to explain the more likely scenario of a late Miocene transition from C3 woodland/ savanna to C4 grasslands. A largely unexplored hypothesis is that climatic changes in late Miocene altered disturbance regimes, in particular the incidence of fires, which today are often associated with maintenance of C4 grasslands. Oceanic charcoal sediments that appear to represent Aeolian deposits from continental wildfires follow a strikingly similar pattern of explosive increase in late Miocene. Climate, CO2, and disturbance are not mutually exclusive explanations and probably all acted in concert to promote the expansion of C4 grasslands. More recently, late Quaternary changes in CO2 may have been responsible for driving major changes in the landscape distribution of C4 species. The theory is sound; however, many of the studies cited in support of this model are open to alternative interpretations, and none has eliminated climatic factors as important selective agents. CAM and C4 evolution required coupling of biochemical pathways with structural changes in photosynthetic tissues, succulence in CAM and Kranz in C4. This was apparently accomplished by piecemeal evolution beginning with mechanisms for recapturing respiratory CO2, although this need not have been so in aquatic CAM species. It has been proposed that the extreme rarity of both pathways in the same plant results from biochemical and structural incompatibilities (Sage 2002). Equally important is the fact that the selective environments are quite different, with CAM evolution thriving on stressful sites inhospitable to C3 species whereas C4 evolution has selected for rapid growth capable of outcompeting associated C3 plants.

Women, Co-occurring Disorders, and Violence Study: evaluation design and study population.

PubMed

McHugo, G J; Kammerer, N; Jackson, E W; Markoff, L S; Gatz, M; Larson, M J; Mazelis, R; Hennigan, K

2005-03-01

The Women, Co-occurring Disorders, and Violence Study (WCDVS) was a multi-site cooperative study to evaluate new service models for women with co-occurring mental health and substance use disorders and a history of physical and/or sexual abuse. Despite common features in the service interventions and evaluation procedures, diversity across the nine sites plus differences introduced by non-random assignment led to numerous methodological challenges. This article describes the design, measurement, and analysis decisions behind the WCDVS and lays the foundation for understanding participant-level outcomes and service costs. This article also describes the study population, as recruited and following attrition at the 6-month follow-up, in order to address the threat of selection bias to inferences drawn from this multi-site study.

Transesterification of diethyl oxalate with phenol over sol-gel MoO(3)/TiO(2) catalysts.

PubMed

Kotbagi, Trupti; Nguyen, Duy Luan; Lancelot, Christine; Lamonier, Carole; Thavornprasert, Kaew-Arpha; Wenli, Zhu; Capron, Mickaël; Jalowiecki-Duhamel, Louise; Umbarkar, Shubhangi; Dongare, Mohan; Dumeignil, Franck

2012-08-01

The transesterification of diethyl oxalate (DEO) with phenol to form diphenyl oxalate (DPO) has been carried out in the liquid phase over very efficient MoO(3)/TiO(2) solid-acid sol-gel catalysts. A selectivity of 100 % with a remarkable maximum yield of 88 % were obtained, which opens the route to downstream phosgene-free processes for the synthesis of polycarbonates. Interpretation of the results of various acidity measurements (NH(3) and pyridine desorption, methanol oxidation as a probe reaction) allowed us to identify the catalytic sites as Lewis acid sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maluangnont, Tosapol, E-mail: tosapol.ma@kmitl.ac.th; Catalytic Chemistry Research Unit, Faculty of Science, King Mongkut's Institute of Technology Ladkrabang, Bangkok 10520; Arsa, Pornanan

2016-06-15

While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O{sup 2−} sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4} as an example. The low basicity (0.04 mmol CO{sub 2}/g) and low desorption temperature (50–300 °C) shown by CO{sub 2}− TPD suggests that O{sup 2−} sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO{sub 2}. The liquid-phase adsorptionmore » study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C{sub 16} acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O{sup 2−} sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast {sup 1}H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C{sub 31} ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at Ti{sup IV} sites was also illustrated. - Graphical abstract: Interlayer basic sites in lepidocrocite titanate, K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4}, lead to an intercalation of palmitic acid with a layer expansion. Display Omitted - Highlights: • K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4} intercalates palmitic acid, forming the occluded potassium salt. • The interlayer expansion is evidenced by PXRD patterns and TEM image. • Two types of basic sites are deduced from ultrafast {sup 1}H MAS NMR. • Lepidocrocite titanate catalyses ketonization of palmitic acid to palmitone and corresponding cracked products.« less

Long-term urban carbon dioxide observations reveal spatial and temporal dynamics related to urban characteristics and growth

DOE PAGES

Mitchell, Logan E.; Lin, John C.; Bowling, David R.; ...

2018-03-05

Cities are concentrated areas of CO 2 emissions and have become the foci of policies for mitigation actions. However, atmospheric measurement networks suitable for evaluating urban emissions over time are scarce. Here we present a unique long-term (decadal) record of CO 2 mole fractions from five sites across Utah’s metropolitan Salt Lake Valley. We examine “excess” CO 2 above background conditions resulting from local emissions and meteorological conditions. We ascribe CO 2 trends to changes in emissions, since we did not find longterm trends in atmospheric mixing proxies. Three contrasting CO 2 trends emerged across urban types: negative trends atmore » a residentialindustrial site, positive trends at a site surrounded by rapid suburban growth, and relatively constant CO 2 over time at multiple sites in the established, residential, and commercial urban core. Analysis of populationwithin the atmospheric footprints of the different sites reveals approximately equal increases in population influencing the observed CO 2, implying a nonlinear relationshipwith CO 2 emissions: Population growth in rural areas that experienced suburban development was associated with increasing emissions while population growth in the developed urban core was associated with stable emissions. Four state-of-the-art global-scale emission inventories also have a nonlinear relationship with population density across the city; however, in contrast to our observations, they all have nearly constant emissions over time. Our results indicate that decadal scale changes in urban CO 2 emissions are detectable through monitoring networks and constitute a valuable approach to evaluate emission inventories and studies of urban carbon cycles.« less

Long-term urban carbon dioxide observations reveal spatial and temporal dynamics related to urban characteristics and growth

NASA Astrophysics Data System (ADS)

Mitchell, Logan E.; Lin, John C.; Bowling, David R.; Pataki, Diane E.; Strong, Courtenay; Schauer, Andrew J.; Bares, Ryan; Bush, Susan E.; Stephens, Britton B.; Mendoza, Daniel; Mallia, Derek; Holland, Lacey; Gurney, Kevin R.; Ehleringer, James R.

2018-03-01

Cities are concentrated areas of CO2 emissions and have become the foci of policies for mitigation actions. However, atmospheric measurement networks suitable for evaluating urban emissions over time are scarce. Here we present a unique long-term (decadal) record of CO2 mole fractions from five sites across Utah’s metropolitan Salt Lake Valley. We examine “excess” CO2 above background conditions resulting from local emissions and meteorological conditions. We ascribe CO2 trends to changes in emissions, since we did not find long-term trends in atmospheric mixing proxies. Three contrasting CO2 trends emerged across urban types: negative trends at a residential-industrial site, positive trends at a site surrounded by rapid suburban growth, and relatively constant CO2 over time at multiple sites in the established, residential, and commercial urban core. Analysis of population within the atmospheric footprints of the different sites reveals approximately equal increases in population influencing the observed CO2, implying a nonlinear relationship with CO2 emissions: Population growth in rural areas that experienced suburban development was associated with increasing emissions while population growth in the developed urban core was associated with stable emissions. Four state-of-the-art global-scale emission inventories also have a nonlinear relationship with population density across the city; however, in contrast to our observations, they all have nearly constant emissions over time. Our results indicate that decadal scale changes in urban CO2 emissions are detectable through monitoring networks and constitute a valuable approach to evaluate emission inventories and studies of urban carbon cycles.

Long-term urban carbon dioxide observations reveal spatial and temporal dynamics related to urban characteristics and growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitchell, Logan E.; Lin, John C.; Bowling, David R.

Cities are concentrated areas of CO 2 emissions and have become the foci of policies for mitigation actions. However, atmospheric measurement networks suitable for evaluating urban emissions over time are scarce. Here we present a unique long-term (decadal) record of CO 2 mole fractions from five sites across Utah’s metropolitan Salt Lake Valley. We examine “excess” CO 2 above background conditions resulting from local emissions and meteorological conditions. We ascribe CO 2 trends to changes in emissions, since we did not find longterm trends in atmospheric mixing proxies. Three contrasting CO 2 trends emerged across urban types: negative trends atmore » a residentialindustrial site, positive trends at a site surrounded by rapid suburban growth, and relatively constant CO 2 over time at multiple sites in the established, residential, and commercial urban core. Analysis of populationwithin the atmospheric footprints of the different sites reveals approximately equal increases in population influencing the observed CO 2, implying a nonlinear relationshipwith CO 2 emissions: Population growth in rural areas that experienced suburban development was associated with increasing emissions while population growth in the developed urban core was associated with stable emissions. Four state-of-the-art global-scale emission inventories also have a nonlinear relationship with population density across the city; however, in contrast to our observations, they all have nearly constant emissions over time. Our results indicate that decadal scale changes in urban CO 2 emissions are detectable through monitoring networks and constitute a valuable approach to evaluate emission inventories and studies of urban carbon cycles.« less

Baseline studies to select the most sound and sensitive sites to install continuous monitoring per sismo-geochemical networks. The case history of the Norcia-Amatrice-Spoleto seismic sequences (2016-2017)

NASA Astrophysics Data System (ADS)

Quattrocchi, F.; Gallo, F.

2017-12-01

The paper review methodologically and historically - in the frame of seismo-geochemical studies in Italy and abroad to select the most "sensitive" sites along active faults, mostly where structural geology is not able to discover "blind" faults or complex fault crossing systems, with maximum fluids-faults interaction. The paper is highlighting the "site specific" case histories and processes helping in networks design, gathered in occasion of strong-moderate earthquakes, gas-burst or groundwater evolution in geothermal-hydrocarbons field during EU projects (i.e., Geochemical Seismic Zonation, 3F-Faults-Fractures-Fluids Corinth). Some concepts are highlighted based on gather experimental data in 25 years: - if the network is in soil gas is necessary a preliminary study on groundwater too, to understand the sectors of shallow aquifers, as "buffer" bodies, more prone to be oversaturated by geogas from depth; a preliminary grid should consider both the CO2-CH4-Rn fluxes, all gas concentrations and isotopes analyses (TDIC, CH4 CO2 , rare gas) case by case described here, mostly where the regional faults are crossing each other and where a carrier gas is acting i.e., CO2. It is very un-correct to install mono-parametric stations, i.e. only Radon to understand the real WRI processes. - if the network is in groundwater is very important a preliminary study before, during and after seismic sequences, to realize where the maximum anomalies (i.e., anomalous animal behavior, temperature increasing, geochemical anomalies, new gas relase) are and will be envisaged, as found for the Umbria-Marche border (the Colfiorito 1997-1998 and the 2016-2017 Norcia-Amatrice seismic sequences), where a deep pore-pressure dominated situation could be constrained by seismo-geochemistry, along "still silent" close fault segments too. if the network is in groundwater is very important a geochemical multidisciplinary approach to constrain the segment length and relative maximum magnitude.

Structural insights into binding of small molecule inhibitors to Enhancer of Zeste Homolog 2

NASA Astrophysics Data System (ADS)

Kalinić, Marko; Zloh, Mire; Erić, Slavica

2014-11-01

Enhancer of Zeste Homolog 2 (EZH2) is a SET domain protein lysine methyltransferase (PKMT) which has recently emerged as a chemically tractable and therapeutically promising epigenetic target, evidenced by the discovery and characterization of potent and highly selective EZH2 inhibitors. However, no experimental structures of the inhibitors co-crystallized to EZH2 have been resolved, and the structural basis for their activity and selectivity remains unknown. Considering the need to minimize cross-reactivity between prospective PKMT inhibitors, much can be learned from understanding the molecular basis for selective inhibition of EZH2. Thus, to elucidate the binding of small-molecule inhibitors to EZH2, we have developed a model of its fully-formed cofactor binding site and used it to carry out molecular dynamics simulations of protein-ligand complexes, followed by molecular mechanics/generalized born surface area calculations. The obtained results are in good agreement with biochemical inhibition data and reflect the structure-activity relationships of known ligands. Our findings suggest that the variable and flexible post-SET domain plays an important role in inhibitor binding, allowing possibly distinct binding modes of inhibitors with only small variations in their structure. Insights from this study present a good basis for design of novel and optimization of existing compounds targeting the cofactor binding site of EZH2.

CO2 capture by polymeric membranes composed of hyper-branched polymers with dense poly(oxyethylene) comb and poly(amidoamine)

NASA Astrophysics Data System (ADS)

Taniguchi, Ikuo; Wada, Norihisa; Kinugasa, Kae; Higa, Mitsuru

2017-11-01

Due to CO2-philic nature of polyoxyethylene (POE), a dense POE comb structure was tethered onto PMMA backbone to develop CO2 separation membranes over N2. The resulting hyper-branched polymers displayed preferential CO2 permeation. When the polymer thin layer was formed on a high gas permeable polydimethylsiloxane (PDMS) support by a spray-coating manner, the resulting thin film composite (TFC) membranes displayed very high CO2 permeability. However, the CO2 selectivity, which was the permeability ratio of CO2 over N2, was moderate and lower than 50. To enhance the selectivity, poly(amidoamine) (PAMAM) was introduced to the hyper-branched polymers in the CO2-selective layer of the TFC membranes. The CO2 selectivity increased from 47 to 90 with increasing PAMAM content to 40 wt%, and it was drastically enhanced to 350 with PAMAM content of 50 wt%. Differential scanning calorimetry (DSC) and laser microscope revealed formation of PAMAM-rich domain at the higher amine content, where CO2 could readily migrate in comparison to the other polymeric fractions.

Highly Active and Selective Hydrogenation of CO2 to Ethanol by Ordered Pd-Cu Nanoparticles.

PubMed

Bai, Shuxing; Shao, Qi; Wang, Pengtang; Dai, Qiguang; Wang, Xingyi; Huang, Xiaoqing

2017-05-24

Carbon dioxide (CO 2 ) hydrogenation to ethanol (C 2 H 5 OH) is considered a promising way for CO 2 conversion and utilization, whereas desirable conversion efficiency remains a challenge. Herein, highly active, selective and stable CO 2 hydrogenation to C 2 H 5 OH was enabled by highly ordered Pd-Cu nanoparticles (NPs). By tuning the composition of the Pd-Cu NPs and catalyst supports, the efficiency of CO 2 hydrogenation to C 2 H 5 OH was well optimized with Pd 2 Cu NPs/P25 exhibiting high selectivity to C 2 H 5 OH of up to 92.0% and the highest turnover frequency of 359.0 h -1 . Diffuse reflectance infrared Fourier transform spectroscopy results revealed the high C 2 H 5 OH production and selectivity of Pd 2 Cu NPs/P25 can be ascribed to boosting *CO (adsorption CO) hydrogenation to *HCO, the rate-determining step for the CO 2 hydrogenation to C 2 H 5 OH.

BOREAS TGB-1 Soil CH4 and CO2 Profile Data from NSA Tower Sites

NASA Technical Reports Server (NTRS)

Crill, Patrick; Varner, Ruth K.; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor)

2000-01-01

The BOREAS TGB-1 team made numerous measurements of trace gas concentrations and fluxes at various NSA sites. This data set contains methane (CH4) and carbon dioxide (CO2) concentrations in soil profiles from the NSA-OJP, NSA-OBS, NSA-YJP, and NSA-BP sites during the period of 23-May to 20-Sep-1994. The soil gas sampling profiles of CH 4 and CO 2 were completed to quantify controls on CO2 and CH4 fluxes in the boreal forest. The data are provided in tabular ASCII files.

Oxidation of CO by NO on planar and faceted Ir(210)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Wenhua; Bartynski, Robert A.; Kaghazchi, Payam

2012-06-11

Oxidation of CO by pre-adsorbed NO has been studied on planar Ir(210) and nanofaceted Ir(210) with average facet sizes of 5 nm and 14 nm by temperature programmed desorption (TPD). Both surfaces favor oxidation of CO to CO 2, which is accompanied by simultaneous reduction of NO with high selectivity to N 2. At low NO pre-coverage, the temperature (T i) for the onset of CO 2 desorption as well as CO 2 desorption peak temperature (T p) decreases with increasing CO exposure, and NO dissociation is affected by co-adsorbed CO. At high NO pre-coverage, T i and T pmore » are independent of CO exposure, and co-adsorbed CO has no influence on dissociation of NO. Moreover, at low NO pre-coverage, planar Ir(210) is more active than faceted Ir(210) for oxidation of CO to CO 2: T i and T p are much lower on planar Ir(210) than that on faceted Ir(210). In addition, faceted Ir(210) with an average facet size of 5 nm is more active for oxidation of CO to CO 2 than faceted Ir(210) with an average facet size of 14 nm, i.e., oxidation of CO by pre-adsorbed NO on faceted Ir(210) exhibits size effects on the nanometer scale. In comparison, at low O pre-coverage planar Ir(210) is more active than faceted Ir(210) for oxidation of CO to CO 2 but no evidence has been found for size effects in oxidation of CO by pre-adsorbed oxygen on faceted Ir(210) for average facet sizes of 5 nm and 14 nm. The TPD data indicate the same reaction pathway for CO 2 formation from CO + NO and CO + O reactions on planar Ir(210). Lastly, the adsorption sites of CO, NO, O, CO + O, and CO + NO on Ir are characterized by density functional theory.« less

Assessing the acidity of high silica chabazite H-SSZ-13 by FTIR using CO as molecular probe: Comparison with H-SAPO-34.

PubMed

Bordiga, Silvia; Regli, Laura; Cocina, Donato; Lamberti, Carlo; Bjørgen, Morten; Lillerud, Karl Petter

2005-02-24

Zeolitic materials based on the chabazite topology, such as H-SAPO-34, possess unique shape-selectivity properties for converting methanol into light olefins. In addition to the topology, zeolite acidity is inherently linked to catalyst activity and selectivity. The acidic properties of high silica chabazite (H-SSZ-13) have attracted much attention in the past decade because the material represents an idealized model system having one acidic site per cage. Conclusions drawn so far have essentially been founded on quantum chemical methods. An experimentally based benchmark of the acidity of H-SSZ-13 has hitherto not been available. In this work, transmission FTIR spectroscopy provides a description of the different acidic sites of H-SSZ-13 by using CO as molecular probe at 70 K. The results demonstrate that H-SSZ-13 is a strongly Brønsted acidic material, essentially having two distinct families of acidic sites. In contrast to numerous preceding reports, we find it fundamental to consider proton distributions among all four possible sites, and do not delimit the interpretations to only two sites. The present data consistently suggest the most abundant family of protons to have three members being located on different crystalline positions on the eight-membered-ring window giving access to the chabazite cage. Consequently, these protons are exposed to two neighboring cages. The second, and less abundant family, is constituted by only one site that is situated on the six-membered ring defining the top/bottom of the barrel-shaped chabazite cage. This proton is therefore only exposed to one cage and requires a higher CO pressure to form adducts. Toward CO, both families of sites possess the same acidity. Parallel experiments were also carried out for the isostructural and commercially important H-SAPO-34 having an equal density of acidic sites. This is the first attempt to directly compare, on an experimental basis, the acidity of these two materials.

The cultivation of energy crops for biogas production and the application of digestates are characterized by high variability of CO2 exchange and soil organic C stock changes

NASA Astrophysics Data System (ADS)

Augustin, Juergen; Fiedler, Sebastian; Heintze, Gawan; Rohwer, Marcus; Prescher, Anne-Katrin; Pohl, Madlen; Jurisch, Nicole; Hagemann, Ulrike

2017-04-01

In Germany, agricultural production accounts for approx. 15% of total anthropogenic greenhouse gas emissions. The cultivation of energy crops is thus considered an important option to reduce the climate impact and maintain or increase soil organic carbon (SOC) stocks. In particular, this applies to the continuously expanding cultivation of energy crops for biogas production and the associated use of residues from anaerobic digestion (digestates) as organic fertilizer. To date, there is only limited and contradicting evidence on the impacts of this management practice on the CO2 exchange as well as the change of SOC stocks. We will present results from a 4-year field study at 5 sites in Germany using identical methods to investigate the interacting effects of i) 3 N-fertilizer treatments including calcium ammonium nitrate and digestates and ii) a crop rotation of 7 energy crops like maize, sorghum, triticale, and wheat on net ecosystem CO2 exchange (NEE) and the change of SOC stocks. We used the manual chamber approach for measuring NEE as the difference between gross primary production and ecosystem respiration. The determination of SOC stock changes was based on a C budget approach, which includes the cumulated annual NEE, the C export by harvest, and the C import by application of anaerobic digestates. The CO2 exchange and the change of SOC stocks were influenced by multiple factors like crop, site, fertilization, and climate, as well as their complex interactions. A large proportion of the variability of the CO2 exchange can be attributed to interannual climatic variability. Productive crops like maize and sorghum generally feature the most intensive CO2 exchange, while less productive crops can compensate for this by means of longer cultivation times. Regardless of the extreme variability, pronounced and partly significant differences of NEE and C budgets between sites were observed. On average, SOC stocks declined over a full crop rotation, but with highly variable positive and negative C budgets. This indicates that, in most cases, neither the selected crops nor the application of anaerobic digestates were sufficient to compensate for SOC losses. Apparently, the potential of anaerobic digestates to maintain or increase SOC stocks is considerably smaller than expected. If continuous decreases of SOC stocks due to energy crop cultivation are to be avoided, additional studies on the optimization of crop rotations (selection of plants with high C input), and digestate fertilization (type of digestate, amount and application technique) are required. A continuously improved version of the methodology used in this study promises faster and more precise results than classic long-term field trials.

Design Support of an Above Cap-rock Early Detection Monitoring System using Simulated Leakage Scenarios at the FutureGen2.0 Site

DOE PAGES

Williams, Mark D.; USA, Richland Washington; Vermuel, Vince R.; ...

2014-12-31

The FutureGen 2.0 Project will design and build a first-of-its-kind, near-zero emissions coal-fueled power plant with carbon capture and storage (CCS). To assess storage site performance and meet the regulatory requirements of the Class VI Underground Injection Control (UIC) Program for CO 2 Geologic Sequestration, the FutureGen 2.0 project will implement a suite of monitoring technologies designed to evaluate CO 2 mass balance and detect any unforeseen loss in CO 2 containment. The monitoring program will include direct monitoring of the reservoir, and early-leak-detection monitoring directly above the primary confining zone. This preliminary modeling study described here focuses on hypotheticalmore » leakage scenarios into the first permeable unit above the primary confining zone (Ironton Sandstone) and is used to support assessment of early-leak detection capabilities. Future updates of the model will be used to assess potential impacts on the lowermost underground source of drinking water (Saint Peter Sandstone) for a range of theoretical leakage scenarios. This preliminary modeling evaluation considers both pressure response and geochemical signals in the overlying Ironton Sandstone. This model is independent of the FutureGen 2.0 reservoir model in that it does not simulate caprock discontinuities, faults, or failure scenarios. Instead this modeling effort is based on theoretical, volumetric-rate based leakage scenarios. The scenarios include leakage of 1% of the total injected CO 2 mass, but spread out over different time periods (20, 100, and 500 years) with each case yielding a different mass flux (i.e., smaller mass fluxes for longer duration leakage cases]. A brine leakage scenario using a volumetric leakage similar to the 20 year 1% CO 2 case was also considered. A framework for the comparison of the various cases was developed based on the exceedance of selected pressure and geochemical thresholds at different distances from the point of leakage and at different vertical positions within the Ironton Sandstone. These preliminary results, and results from an updated models that incorporate additional site-specific characterization data, support development/refinement of the monitoring system design.« less

Carbon Dioxide Extraction from the Atmosphere Through Engineered Chemical Sinkage: Enabling Energy and Environmental Security

NASA Astrophysics Data System (ADS)

Dubey, M. K.; Ziock, H.; Rueff, G.; Smith, W. S.; Colman, J.; Elliott, S.; Lackner, K.; Johnston, N. A.

2002-05-01

We present the case for carbon dioxide (CO2) extraction from air using engineered chemical sinks as a means of sustaining fossil energy use by avoiding climate change. Existing carbon sequestration strategies such as CO2 injection into geologic formations or the deep ocean and mineral carbonation, require a pure stream of concentrated CO2 to be viable. Furthermore, current emphasis on reducing the global CO2 emissions is on large centralized power plants. However, more than half of all emissions are from the transportation sector and small, distributed sources such as home heating, etc. Most solutions for dealing with these sources explicitly or implicitly entail completely overhauling the existing infrastructure. To solve these problems, Los Alamos National Laboratory has conceived a novel approach for directly extracting CO2 from the atmosphere. Direct extraction converts the dilute CO2 (370 parts per million) in the atmosphere into a pure CO2 stream ready for permanent sequestration. It provides the following advantages: (1) Preserves our existing energy use and fuel distribution systems, which represent a large investment, (2) Indirectly captures CO2 from the myriad of small, distributed, and mobile sources that otherwise are not accessible to sequestration, (3) Allows atmospheric CO2 levels to be restored to their pre-industrial age value, (4) Provides free transport of CO2 to suitable sequestration sites by using natural atmospheric circulation, and (5) Is relatively compact and therefore inexpensive when compared to renewable concepts. Our concept harnesses atmospheric circulation to transport CO2 to sites where the CO2 is extracted by binding it to an adsorbent. The bound CO2 is then recovered as pure gas by heating together with the solid adsorbent that is recycled. As a proof of concept, we show that an aqueous Ca(OH)2 solution efficiently converts CO2 to a CaCO3 solid that can be heated to obtain pure CO2 and recover the CaO. Even with recycling costs, CO2 extraction from air blown by wind through a 1 m2 aperture could eliminate the greenhouse gas impact of a 100 kW gasoline engine, making it more favorable than renewable sources such as solar, wind, or bio-mass. We report economic and scaling arguments, atmospheric simulations and laboratory experiments on candidate adsorbents that support pursuing air-extraction as an advanced CO2 capture technology. We assess and guide synthetic advances in tailoring zeolites, amines, carbon, and ionic fluids to adsorb CO2 selectively, rapidly, and gently enough to facilitate recovery, that promise to significantly enhance the efficiency of CO2 air extraction. This method could process today's world output of CO2 at costs of about 5 cents/liter of gasoline, a manageable scale for this massive undertaking.

Amino acid screening based on structural modeling identifies critical residues for the function, ion selectivity and structure of Arabidopsis MTP1.

PubMed

Kawachi, Miki; Kobae, Yoshihiro; Kogawa, Sayaka; Mimura, Tetsuro; Krämer, Ute; Maeshima, Masayoshi

2012-07-01

Arabidopsis thaliana MTP1 is a vacuolar membrane Zn(2+)/H(+) antiporter of the cation diffusion facilitator family. Here we present a structure-function analysis of AtMTP1-mediated transport and its remarkable Zn(2+) selectivity by functional complementation tests of more than 50 mutant variants in metal-sensitive yeast strains. This was combined with homology modeling of AtMTP1 based on the crystal structure of the Escherichia coli broad-specificity divalent cation transporter YiiP. The Zn(2+)-binding sites of EcYiiP in the cytoplasmic C-terminus, and the pore formed by transmembrane helices TM2 and TM5, are conserved in AtMTP1. Although absent in EcYiiP, Cys31 and Cys36 in the extended N-terminal cytosolic domain of AtMTP1 are necessary for complementation of a Zn-sensitive yeast strain. On the cytosolic side of the active Zn(2+)-binding site inside the transmembrane pore, Ala substitution of either Asn258 in TM5 or Ser101 in TM2 non-selectively enhanced the metal tolerance conferred by AtMTP1. Modeling predicts that these residues obstruct the movement of cytosolic Zn(2+) into the intra-membrane Zn(2+)-binding site of AtMTP1. A conformational change in the immediately preceding His-rich cytosolic loop may displace Asn258 and permit Zn(2+) entry into the pore. This would allow dynamic coupling of Zn(2+) transport to the His-rich loop, thus acting as selectivity filter or sensor of cytoplasmic Zn(2+) levels. Individual mutations at diverse sites within AtMTP1 conferred Co and Cd tolerance in yeast, and included deletions in N-terminal and His-rich intra-molecular cytosolic domains, and mutations of single residues flanking the transmembrane pore or participating in intra- or inter-molecular domain interactions, all of which are not conserved in the non-selective EcYiiP. © 2012 The Authors Journal compilation © 2012 FEBS.

The Transmembrane Region of Guard Cell SLAC1 Channels Perceives CO2 Signals via an ABA-Independent Pathway in Arabidopsis.

PubMed

Yamamoto, Yoshiko; Negi, Juntaro; Wang, Cun; Isogai, Yasuhiro; Schroeder, Julian I; Iba, Koh

2016-02-01

The guard cell S-type anion channel, SLOW ANION CHANNEL1 (SLAC1), a key component in the control of stomatal movements, is activated in response to CO2 and abscisic acid (ABA). Several amino acids existing in the N-terminal region of SLAC1 are involved in regulating its activity via phosphorylation in the ABA response. However, little is known about sites involved in CO2 signal perception. To dissect sites that are necessary for the stomatal CO2 response, we performed slac1 complementation experiments using transgenic plants expressing truncated SLAC1 proteins. Measurements of gas exchange and stomatal apertures in the truncated transgenic lines in response to CO2 and ABA revealed that sites involved in the stomatal CO2 response exist in the transmembrane region and do not require the SLAC1 N and C termini. CO2 and ABA regulation of S-type anion channel activity in guard cells of the transgenic lines confirmed these results. In vivo site-directed mutagenesis experiments targeted to amino acids within the transmembrane region of SLAC1 raise the possibility that two tyrosine residues exposed on the membrane are involved in the stomatal CO2 response. © 2016 American Society of Plant Biologists. All rights reserved.

The Transmembrane Region of Guard Cell SLAC1 Channels Perceives CO2 Signals via an ABA-Independent Pathway in Arabidopsis

PubMed Central

Yamamoto, Yoshiko; Negi, Juntaro; Isogai, Yasuhiro; Schroeder, Julian I.; Iba, Koh

2016-01-01

The guard cell S-type anion channel, SLOW ANION CHANNEL1 (SLAC1), a key component in the control of stomatal movements, is activated in response to CO2 and abscisic acid (ABA). Several amino acids existing in the N-terminal region of SLAC1 are involved in regulating its activity via phosphorylation in the ABA response. However, little is known about sites involved in CO2 signal perception. To dissect sites that are necessary for the stomatal CO2 response, we performed slac1 complementation experiments using transgenic plants expressing truncated SLAC1 proteins. Measurements of gas exchange and stomatal apertures in the truncated transgenic lines in response to CO2 and ABA revealed that sites involved in the stomatal CO2 response exist in the transmembrane region and do not require the SLAC1 N and C termini. CO2 and ABA regulation of S-type anion channel activity in guard cells of the transgenic lines confirmed these results. In vivo site-directed mutagenesis experiments targeted to amino acids within the transmembrane region of SLAC1 raise the possibility that two tyrosine residues exposed on the membrane are involved in the stomatal CO2 response. PMID:26764376

Post-Synthetic Modification of Porphyrin-Encapsulating Metal-Organic Materials by Cooperative Addition of Inorganic Salts to Enhance CO 2/CH 4 Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Zhenjie; Gao, Wen-Yang; Wojtas, Lukasz

Keeping MOM: Reaction of biphenyl-3,4',5-tricarboxylate and Cd(NO 3) 2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate afforded porph@MOM-11, a microporous metal–organic material (MOM) that encapsulates cationic porphyrins and solvent in alternating open channels. Porph@MOM-11 has cation and anion binding sites that facilitate cooperative addition of inorganic salts (such as M +Cl -) in a stoichiometric fashion.

Carbon dioxide flux and net primary production of a boreal treed bog: Responses to warming and water-table-lowering simulations of climate change

NASA Astrophysics Data System (ADS)

Munir, T. M.; Perkins, M.; Kaing, E.; Strack, M.

2015-02-01

Midlatitude treed bogs represent significant carbon (C) stocks and are highly sensitive to global climate change. In a dry continental treed bog, we compared three sites: control, recent (1-3 years; experimental) and older drained (10-13 years), with water levels at 38, 74 and 120 cm below the surface, respectively. At each site we measured carbon dioxide (CO2) fluxes and estimated tree root respiration (Rr; across hummock-hollow microtopography of the forest floor) and net primary production (NPP) of trees during the growing seasons (May to October) of 2011-2013. The CO2-C balance was calculated by adding the net CO2 exchange of the forest floor (NEff-Rr) to the NPP of the trees. From cooler and wetter 2011 to the driest and the warmest 2013, the control site was a CO2-C sink of 92, 70 and 76 g m-2, the experimental site was a CO2-C source of 14, 57 and 135 g m-2, and the drained site was a progressively smaller source of 26, 23 and 13 g CO2-C m-2. The short-term drainage at the experimental site resulted in small changes in vegetation coverage and large net CO2 emissions at the microforms. In contrast, the longer-term drainage and deeper water level at the drained site resulted in the replacement of mosses with vascular plants (shrubs) on the hummocks and lichen in the hollows leading to the highest CO2 uptake at the drained hummocks and significant losses in the hollows. The tree NPP (including above- and below-ground growth and litter fall) in 2011 and 2012 was significantly higher at the drained site (92 and 83 g C m-2) than at the experimental (58 and 55 g C m-2) and control (52 and 46 g C m-2) sites. We also quantified the impact of climatic warming at all water table treatments by equipping additional plots with open-top chambers (OTCs) that caused a passive warming on average of ~ 1 °C and differential air warming of ~ 6 °C at midday full sun over the study years. Warming significantly enhanced shrub growth and the CO2 sink function of the drained hummocks (exceeding the cumulative respiration losses in hollows induced by the lowered water level × warming). There was an interaction of water level with warming across hummocks that resulted in the largest net CO2 uptake at the warmed drained hummocks. Thus in 2013, the warming treatment enhanced the sink function of the control site by 13 g m-2, reduced the source function of the experimental by 10 g m-2 and significantly enhanced the sink function of the drained site by 73 g m-2. Therefore, drying and warming in continental bogs is expected to initially accelerate CO2-C losses via ecosystem respiration, but persistent drought and warming is expected to restore the peatland's original CO2-C sink function as a result of the shifts in vegetation composition and productivity between the microforms and increased NPP of trees over time.

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE PAGES

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.; ...

2018-05-28

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Gas separation performance of carbon molecular sieve membranes based on 6FDA-mPDA/DABA (3:2) polyimide.

PubMed

Qiu, Wulin; Zhang, Kuang; Li, Fuyue Stephanie; Zhang, Ke; Koros, William J

2014-04-01

6FDA-mPDA/DABA (3:2) polyimide was synthesized and characterized for uncross-linked, thermally crosslinked, and carbon molecular sieve (CMS) membranes. The membranes were characterized with thermogravimetric analysis, FTIR spectroscopy, wide-angle X-ray diffraction, and gas permeation tests. Variations in the d spacing, the formation of pore structures, and changes in the pore sizes of the CMS membranes were discussed in relation to pyrolysis protocols. The uncross-linked polymer membranes showed high CO2 /CH4 selectivity, whereas thermally crosslinked membranes exhibited significantly improved CO2 permeability and excellent CO2 plasticization resistance. The CMS membranes showed even higher CO2 permeability and CO2 /CH4 selectivity. An increase in the pyrolysis temperature resulted in CMS membranes with lower gas permeability but higher selectivity. The 550 °C pyrolyzed CMS membranes showed CO2 permeability as high as 14 750 Barrer with CO2 /CH4 selectivity of approximately 52. Even 800 °C pyrolyzed CMS membranes still showed high CO2 permeability of 2610 Barrer with high CO2 /CH4 selectivity of approximately 118. Both polymer membranes and the CMS membranes are very attractive in aggressive natural gas purification applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrahigh and Selective SO2 Uptake in Inorganic Anion-Pillared Hybrid Porous Materials.

PubMed

Cui, Xili; Yang, Qiwei; Yang, Lifeng; Krishna, Rajamani; Zhang, Zhiguo; Bao, Zongbi; Wu, Hui; Ren, Qilong; Zhou, Wei; Chen, Banglin; Xing, Huabin

2017-07-01

The efficient capture of SO 2 is of great significance in gas-purification processes including flue-gas desulfurization and natural-gas purification, but the design of porous materials with high adsorption capacity and selectivity of SO 2 remains very challenging. Herein, the selective recognition and dense packing of SO 2 clusters through multiple synergistic host-guest and guest-guest interactions by controlling the pore chemistry and size in inorganic anion (SiF 6 2- , SIFSIX) pillared metal-organic frameworks is reported. The binding sites of anions and aromatic rings in SIFSIX materials grasp every atom of SO 2 firmly via S δ+ ···F δ- electrostatic interactions and O δ- ···H δ+ dipole-dipole interactions, while the guest-guest interactions between SO 2 molecules further promote gas trapping within the pore space, which is elucidated by first-principles density functional theory calculations and powder X-ray diffraction experiments. These interactions afford new benchmarks for the highly efficient removal of SO 2 from other gases, even if at a very low SO 2 concentration. Exceptionally high SO 2 capacity of 11.01 mmol g -1 is achieved at atmosphere pressure by SIFSIX-1-Cu, and unprecedented low-pressure SO 2 capacity is obtained in SIFSIX-2-Cu-i (4.16 mmol g -1 SO 2 at 0.01 bar and 2.31 mmol g -1 at 0.002 bar). More importantly, record SO 2 /CO 2 selectivity (86-89) and excellent SO 2 /N 2 selectivity (1285-3145) are also achieved. Experimental breakthrough curves further demonstrate the excellent performance of these hybrid porous materials in removing low-concentration SO 2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphological and biochemical changes in Azadirachta indica from coal combustion fly ash dumping site from a thermal power plant in Delhi, India.

PubMed

Qadir, Sami Ullah; Raja, Vaseem; Siddiqui, Weqar A

2016-07-01

The foliar and biochemical traits of Azadirachta indica A. Juss from fly ash (FA) dumping site in Badarpur thermal power plant (BTPP) New Delhi, India was studied. Three different experimental sites were selected at different distances from the thermal power plant. Ambient suspended particulate matter (SPM) and plant responses such as leaf pigments (chlorophyll a, chlorophyll b, and carotenoids), total chlorophyll, net photosynthetic rate, stomatal index (SI), stomatal conductance (SC), intercellular carbon dioxide concentration [CO2]i, net photosynthetic rate (NPR), nitrogen, nitrate, nitrate reductase activity, proline, protein, reducing sugar and sulphur content were measured. Considerable reduction in pigments (chlorophyll a, chlorophyll b and carotenoids), and total chlorophyll was observed at fly ash dumping site. Fly ash stress revealed the inhibitory effect on Nitrate reductase activity (NRA), Nitrate, soluble protein, and reducing sugar content, whereas stimulatory effect was found for the stomatal index, nitrogen, proline, antioxidants and sulphur content in the leaves. Under fly ash stress, stomatal conductance was low, leading to declining in photosynthetic rate and increase in the internal CO2 concentration of leaf. Single leaf area (SLA), leaf length and leaf width also showed a declining trend from control to the polluted site. Antioxidant enzymes increased in leaves reflecting stress and extenuation of reactive oxygen species (ROS). Copyright © 2016 Elsevier Inc. All rights reserved.

Complementary Phosphorylation Sites in the Adaptor Protein SLP-76 Promote Synergistic Activation of Natural Killer Cells

PubMed Central

Kim, Hun Sik; Long, Eric O.

2013-01-01

The cytotoxic effects of natural killer (NK) cells and their ability to secrete cytokines require the induction of synergistic signals from co-activation receptors, such as CD314 (NKG2D) and CD244 (2B4), which bind to ligands expressed on target cells. Synergy is required to overcome inhibition of the guanine nucleotide exchange factor (GEF) Vav1, a central regulator of NK cell activation, by the E3 ubiquitin ligase c-Cbl. However, the molecular basis for this synergy is unknown. Here, we showed that the adaptor protein Src homology 2 (SH2) domain–containing leukocyte phosphoprotein of 76 kD (SLP-76) was required for this synergy, and that distinct tyrosine residues in SLP-76 were phosphorylated by each receptor of a synergistic pair. Selective phosphorylation of tyrosine 113 or tyrosine 128 in SLP-76, each of which enables binding of SLP-76 to Vav1, was unique to receptors that stimulate ligand-dependent target cell killing, because antibody-dependent stimulation by Fc receptor CD16 promoted phosphorylation at both sites. Knockdown and reconstitution experiments with SLP-76 showed the distinct role of each tyrosine in the synergistic mobilization of Ca2+, revealing an unexpected degree of selectivity in the phosphorylation of SLP-76 by NK cell co-activation receptors. Together, these data suggest that complementation of separate phospho-tyrosine targets in SLP-76 forms the basis of synergistic NK cell activation. PMID:22786724

New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

PubMed

Burant, Aniela; Thompson, Christopher; Lowry, Gregory V; Karamalidis, Athanasios K

2016-05-17

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set.

New Linear Partitioning Models Based on Experimental Water: Supercritical CO 2 Partitioning Data of Selected Organic Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burant, Aniela; Thompson, Christopher; Lowry, Gregory V.

2016-05-17

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch reactor system with dual spectroscopic detectors: a near infrared spectrometer for measuring the organic analyte in the CO2 phase, and a UV detector for quantifying the analyte inmore » the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly-parameter linear free energy relationship and to develop five new linear free energy relationships for predicting water-sc-CO2 partitioning coefficients. Four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than the model built for the entire dataset.« less

Pd@H yWO3- x Nanowires Efficiently Catalyze the CO2 Heterogeneous Reduction Reaction with a Pronounced Light Effect.

PubMed

Li, Young Feng; Soheilnia, Navid; Greiner, Mark; Ulmer, Ulrich; Wood, Thomas; Jelle, Abdinoor A; Dong, Yuchan; Yin Wong, Annabelle Po; Jia, Jia; Ozin, Geoffrey A

2018-06-01

The design of photocatalysts able to reduce CO 2 to value-added chemicals and fuels could enable a closed carbon circular economy. A common theme running through the design of photocatalysts for CO 2 reduction is the utilization of semiconductor materials with high-energy conduction bands able to generate highly reducing electrons. Far less explored in this respect are low-energy conduction band materials such as WO 3 . Specifically, we focus attention on the use of Pd nanocrystal decorated WO 3 nanowires as a heretofore-unexplored photocatalyst for the hydrogenation of CO 2 . Powder X-ray diffraction, thermogravimetric analysis, ultraviolet-visible-near infrared, and in situ X-ray photoelectron spectroscopy analytical techniques elucidate the hydrogen tungsten bronze, H y WO 3- x , as the catalytically active species formed via the H 2 spillover effect by Pd. The existence in H y WO 3- x of Brønsted acid hydroxyls OH, W(V) sites, and oxygen vacancies (V O ) facilitate CO 2 capture and reduction reactions. Under solar irradiation, CO 2 reduction attains CO production rates as high as 3.0 mmol g cat -1 hr -1 with a selectivity exceeding 99%. A combination of reaction kinetic studies and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements provide a valuable insight into thermochemical compared to photochemical surface reaction pathways, considered responsible for the hydrogenation of CO 2 by Pd@H y WO 3- x .

DOE Office of Scientific and Technical Information (OSTI.GOV)

Birkholzer, Jens; Apps, John; Zheng, Liange

One promising approach to reduce greenhouse gas emissions is injecting CO{sub 2} into suitable geologic formations, typically depleted oil/gas reservoirs or saline formations at depth larger than 800 m. Proper site selection and management of CO{sub 2} storage projects will ensure that the risks to human health and the environment are low. However, a risk remains that CO{sub 2} could migrate from a deep storage formation, e.g. via local high-permeability pathways such as permeable faults or degraded wells, and arrive in shallow groundwater resources. The ingress of CO{sub 2} is by itself not typically a concern to the water qualitymore » of an underground source of drinking water (USDW), but it will change the geochemical conditions in the aquifer and will cause secondary effects mainly induced by changes in pH, in particular the mobilization of hazardous inorganic constituents present in the aquifer minerals. Identification and assessment of these potential effects is necessary to analyze risks associated with geologic sequestration of CO{sub 2}. This report describes a systematic evaluation of the possible water quality changes in response to CO{sub 2} intrusion into aquifers currently used as sources of potable water in the United States. Our goal was to develop a general understanding of the potential vulnerability of United States potable groundwater resources in the event of CO{sub 2} leakage. This goal was achieved in two main tasks, the first to develop a comprehensive geochemical model representing typical conditions in many freshwater aquifers (Section 3), the second to conduct a systematic reactive-transport modeling study to quantify the effect of CO{sub 2} intrusion into shallow aquifers (Section 4). Via reactive-transport modeling, the amount of hazardous constituents potentially mobilized by the ingress of CO{sub 2} was determined, the fate and migration of these constituents in the groundwater was predicted, and the likelihood that drinking water standards might be exceeded was evaluated. A variety of scenarios and aquifer conditions was considered in a sensitivity evaluation. The scenarios and conditions simulated in Section 4, in particular those describing the geochemistry and mineralogy of potable aquifers, were selected based on the comprehensive geochemical model developed in Section 3.« less

Two-scale evaluation of remediation technologies for a contaminated site by applying economic input-output life cycle assessment: risk-cost, risk-energy consumption and risk-CO2 emission.

PubMed

Inoue, Yasushi; Katayama, Arata

2011-09-15

A two-scale evaluation concept of remediation technologies for a contaminated site was expanded by introducing life cycle costing (LCC) and economic input-output life cycle assessment (EIO-LCA). The expanded evaluation index, the rescue number for soil (RN(SOIL)) with LCC and EIO-LCA, comprises two scales, such as risk-cost, risk-energy consumption or risk-CO(2) emission of a remediation. The effectiveness of RN(SOIL) with LCC and EIO-LCA was examined in a typical contamination and remediation scenario in which dieldrin contaminated an agricultural field. Remediation was simulated using four technologies: disposal, high temperature thermal desorption, biopile and landfarming. Energy consumption and CO(2) emission were determined from a life cycle inventory analysis using monetary-based intensity based on an input-output table. The values of RN(SOIL) based on risk-cost, risk-energy consumption and risk-CO(2) emission were calculated, and then rankings of the candidates were compiled according to RN(SOIL) values. A comparison between three rankings showed the different ranking orders. The existence of differences in ranking order indicates that the scales would not have reciprocal compatibility for two-scale evaluation and that each scale should be used independently. The RN(SOIL) with LCA will be helpful in selecting a technology, provided an appropriate scale is determined. Copyright © 2011 Elsevier B.V. All rights reserved.

Geomechanical Framework for Secure CO 2 Storage in Fractured Reservoirs and Caprocks for Sedimentary Basins in theMidwest United States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sminchak, Joel

This report presents final technical results for the project Geomechanical Framework for Secure CO 2 Storage in Fractured Reservoirs and Caprocks for Sedimentary Basins in the Midwest United States (DE-FE0023330). The project was a three-year effort consisting of seven technical tasks focused on defining geomechanical factors for CO 2 storage applications in deep saline rock formations in Ohio and the Midwest United States, because geomechancial issues have been identified as a significant risk factor for large-scale CO 2 storage applications. A basin-scale stress-strain analysis was completed to describe the geomechanical setting for rock formations of Ordovician-Cambrian age in Ohio andmore » adjacent areas of the Midwest United States in relation to geologic CO 2 storage applications. The tectonic setting, stress orientation-magnitude, and geomechanical and petrophysical parameters for CO 2 storage zones and caprocks in the region were cataloged. Ten geophysical image logs were analyzed for natural fractures, borehole breakouts, and drilling-induced fractures. The logs indicated mostly less than 10 fractures per 100 vertical feet in the borehole, with mostly N65E principal stress orientation through the section. Geophysical image logs and other logs were obtained for three wells located near the sites where specific models were developed for geomechanical simulations: Arches site in Boone County, Kentucky; Northern Appalachian Basin site in Chautauqua County, New York; and E-Central Appalachian Basin site in Tuscarawas County, Ohio. For these three wells, 9,700 feet of image logs were processed and interpreted to provide a systematic review of the distribution within each well of natural fractures, wellbore breakouts, faults, and drilling induced fractures. There were many borehole breakouts and drilling-induced tensile fractures but few natural fractures. Concentrated fractures were present at the Rome-basal sandstone and basal sandstone-Precambrian contacts at the Arches and East-Central Appalachian Basin sites. Geophysical logs were utilized to develop local-scale geologic models by determining geomechanical and petrophysical parameters within the geologic formations. These data were ported to coupled fluid-flow and reservoir geomechanics multi-phase CO 2 injection simulations. The models were developed to emphasize the geomechanical layers within the CO 2 storage zones and caprocks. A series of simulations were completed for each site to evaluate whether commercial-scale CO 2 could be safely injected into each site, given site-specific geologic and geomechanical controls. This involved analyzing the simulation results for the integrity of the caprock, intermediate, and reservoir zones, as well quantifying the areal uplift at the surface. Simulation results were also examined to ensure that the stress-stress perturbations were isolated within the subsurface, and that there was only limited upward migration of the CO 2. Simulations showed capacity to inject more than 10 million metric tons of CO 2 in a single well at the Arches and East Central Appalachian Basin sites without excessive geomechanical risks. Low-permeability rock layers at the Northern Appalachian Basin study area well resulted in very low CO 2 injection capacity. Fracture models developed for the sites suggests that the sites have sparse fracture network in the deeper Cambrian rocks. However, there were indicators in image logs of a moderate fracture matrix in the Rose Run Sandstone at the Northern Appalachian Basin site. Dual permeability fracture matrix simulations suggest the much higher injection rates may be feasible in the fractured interval. Guidance was developed for geomechanical site characterization in the areas of geophysical logging, rock core testing, well testing, and site monitoring. The guidance demonstrates that there is a suitable array of options for addressing geomechanical issues at CO 2 storage sites. Finally, a review of Marcellus and Utica-Point Pleasant shale gas wells and CO 2 storage intervals indicates that these items are vertically separated, except for the Oriskany sandstone and Marcellus wells in southwest Pennsylvania and northern West Virginia. Together, project results present a more realistic portrayal of geomechanical risk factors related to CO 2 storage for existing and future coal-fired power plants in Ohio.« less

The spatial distribution of fossil fuel CO2 traced by Δ(14)C in the leaves of gingko (Ginkgo biloba L.) in Beijing City, China.

PubMed

Niu, Zhenchuan; Zhou, Weijian; Zhang, Xiaoshan; Wang, Sen; Zhang, Dongxia; Lu, Xuefeng; Cheng, Peng; Wu, Shugang; Xiong, Xiaohu; Du, Hua; Fu, Yunchong

2016-01-01

Atmospheric fossil fuel CO2 (CO2ff ) information is an important reference for local government to formulate energy-saving and emission reduction in China. The CO2ff spatial distribution in Beijing City was traced by Δ(14)C in the leaves of gingko (Ginkgo biloba L.) from late March to September in 2009. The Δ(14)C values were in the range of -35.2 ± 2.8∼15.5 ± 3.2 ‰ (average 3.4 ± 11.8 ‰), with high values found at suburban sites (average 12.8 ± 3.1 ‰) and low values at road sites (average -8.4 ± 18.1 ‰). The CO2ff concentrations varied from 11.6 ± 3.7 to 32.5 ± 9.0 ppm, with an average of 16.4 ± 4.9 ppm. The CO2ff distribution in Beijing City showed spatial heterogeneity. CO2ff hotspots were found at road sites resulted from the emission from vehicles, while low CO2ff concentrations were found at suburban sites because of the less usage of fossil fuels. Additionally, CO2ff concentrations in the northwest area were generally higher than those in the southeast area due to the disadvantageous topography.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

PubMed

Luo, Shuangjiang; Stevens, Kevin A; Park, Jae Sung; Moon, Joshua D; Liu, Qiang; Freeman, Benny D; Guo, Ruilan

2016-01-27

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.

Full Life Cycle Research at the Ketzin Pilot Site, Germany - From Safe and Successful CO2 Injection Operation to Post-Injection Monitoring and Site Closure

NASA Astrophysics Data System (ADS)

Liebscher, A. H.

2016-12-01

The Ketzin pilot site near Berlin, Germany, was initiated in 2004 as the first European onshore storage project for research and development on geological CO2 storage. The operational CO2 injection period started in June 2008 and ended in August 2013 when the site entered the post-injection closure period. During these five years, a total amount of 67 kt of CO2 was safely injected into a saline aquifer (Upper Triassic sandstone) at a depth of 630 m - 650 m. In fall 2013, the first observation well was partially plugged in the reservoir section; full abandonment of this well finished in 2015 after roughly 2 years of well closure monitoring. Abandonment of the remaining 4 wells will be finished by 2017 and hand-over of liability to the competent authority is planned for end of 2017. The CO2 injected was mainly of food grade quality (purity > 99.9%). In addition, 1.5 kt of CO2 from the pilot capture facility "Schwarze Pumpe" (oxyfuel power plant CO2 with purity > 99.7%) was injected in 2011. The injection period terminated with a CO2-N2 co-injection experiment of 650 t of a 95% CO2/5% N2 mixture in summer 2013 to study the effects of impurities in the CO2 stream on the injection operation. During regular operation, the CO2 was pre-heated on-site to 40 - 45°C prior to injection to ensure a single-phase injection process and avoid any phase transition or transient states within the injection facility or the reservoir. Between March and July 2013, just prior to the CO2-N2 co-injection experiment, the injection temperature was stepwise decreased down to 10°C within a "cold-injection" experiment to study the effects of two-phase injection conditions. During injection operation, the combination of different geochemical and geophysical monitoring methods enabled detection and mapping of the spatial and temporal in-reservoir behaviour of the injected CO2 even for small quantities. After the cessation of CO2 injection, post-injection monitoring continued and two additional field experiments have been performed. A CO2 back-production experiment was run in autumn 2014 to study the physicochemical properties of the back-produced CO2 as well as the pressure response of the reservoir. In October 2015 to January 2016, a brine injection experiment studied the imbibition process and residual gas saturation.

Surface geothermal exploration in the Canary Islands by means of soil CO_{2} degassing surveys

NASA Astrophysics Data System (ADS)

García-Merino, Marta; Rodríguez, Fátima; Padrón, Eleazar; Melián, Gladys; Asensio-Ramos, María; Barrancos, José; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

With the exception of the Teide fumaroles, there is not any evidence of hydrothermal fluid discharges in the surficial environment of the Canary Islands, the only Spanish territory with potential high enthalpy geothermal resources. Here we show the results of several diffuse CO2 degassing surveys carried out at five mining licenses in Tenerife and Gran Canaria with the aim of sorting the possible geothermal potential of these five mining licenses. The primary objective of the study was to reduce the uncertainty inherent to the selection of the areas with highest geothermal potential for future exploration works. The yardstick used to classify the different areas was the contribution of volcano-hydrothermal CO2 in the diffuse CO2 degassing at each study area. Several hundreds of measurements of diffuse CO2 emission, soil CO2 concentration and isotopic composition were performed at each mining license. Based in three different endmembers (biogenic, atmospheric and deep-seated CO2) with different CO2 concentrations (100, 0.04 and 100%, respectively) and isotopic compositions (-24, -8 and -3 per mil vs. VPDB respectively) a mass balance to distinguish the different contribution of each endmember in the soil CO2 at each sampling site was made. The percentage of the volcano-hydrothermal contribution in the current diffuse CO2 degassing was in the range 0-19%. The Abeque mining license, that comprises part of the north-west volcanic rift of Tenerife, seemed to show the highest geothermal potential, with an average of 19% of CO2 being released from deep sources, followed by Atidama (south east of Gran Canaria) and Garehagua (southern volcanic rift of Tenerife), with 17% and 12% respectively.

Detection of CO2 leaks from carbon capture and storage sites to the atmosphere with combined CO2 and O2 measurements

NASA Astrophysics Data System (ADS)

van Leeuwen, Charlotte; Meijer, Harro A. J.

2015-04-01

One of the main issues in carbon capture and storage (CCS) is the possibility of leakage of CO2 from the storage reservoir to the atmosphere, both from a public health and a climate change combat perspective. Detecting these leaks in the atmosphere is difficult due to the rapid mixing of the emitted CO2 with the surrounding air masses and the high natural variability of the atmospheric CO2 concentration. Instead of measuring only the CO2 concentration of the atmosphere, its isotopes or chemical tracers that are released together with the CO2, our method uses O2 measurements in addition to CO2 measurements to detect a leak from a CCS site. CO2 and O2 are coupled in most processes on earth. In photosynthesis, plants take up CO2 and release O2 at the same time. In respiration and fossil fuel burning, O2 is consumed while CO2 is released. In case of a leak from a CCS site, however, there is no relationship between CO2 and O2. A CO2 leak can therefore be distinguished from other sources of CO2 by looking at the atmospheric CO2-O2 ratio. A natural increase of the CO2 concentration is accompanied by a drop in the O2 concentration, while an increase in the CO2 concentration caused by a leak from a CCS site does not have any effect on the O2 concentration. To demonstrate this leak detection strategy we designed and built a transportable CO2 and O2 measurement system, that is capable of measuring the relatively minute (ppm's variations on a 21% concentration) changes in the O2 concentration. The system comprises of three cases that contain the instrumentation and gas handling equipment, the gas cylinders used as reference and calibration gases and a drying system, respectively. Air is pumped to the system from an air inlet that is placed in a small tower in the field. At the conference, we will demonstrate the success of leak detection with our system by showing measurements of several CO2 release experiments, where CO2 was released at a small distance from the air inlet of our instrument.

Annual sums of carbon dioxide exchange over a heterogeneous urban landscape through machine learning based gap-filling

NASA Astrophysics Data System (ADS)

Menzer, Olaf; Meiring, Wendy; Kyriakidis, Phaedon C.; McFadden, Joseph P.

2015-01-01

A small, but growing, number of flux towers in urban environments measure surface-atmospheric exchanges of carbon dioxide by the eddy covariance method. As in all eddy covariance studies, obtaining annual sums of urban CO2 exchange requires imputation of data gaps due to low turbulence and non-stationary conditions, adverse weather, and instrument failures. Gap-filling approaches that are widely used for measurements from towers in natural vegetation are based on light and temperature response models. However, they do not account for key features of the urban environment including tower footprint heterogeneity and localized CO2 sources. Here, we present a novel gap-filling modeling framework that uses machine learning to select explanatory variables, such as continuous traffic counts and temporal variables, and then constrains models separately for spatially classified subsets of the data. We applied the modeling framework to a three year time series of measurements from a tall broadcast tower in a suburban neighborhood of Minneapolis-Saint Paul, Minnesota, USA. The gap-filling performance was similar to that reported for natural measurement sites, explaining 64% to 88% of the variability in the fluxes. Simulated carbon budgets were in good agreement with an ecophysiological bottom-up study at the same site. Total annual carbon dioxide flux sums for the tower site ranged from 1064 to 1382 g C m-2 yr-1, across different years and different gap-filling methods. Bias errors of annual sums resulting from gap-filling did not exceed 18 g C m-2 yr-1 and random uncertainties did not exceed ±44 g C m-2 yr-1 (or ±3.8% of the annual flux). Regardless of the gap-filling method used, the year-to-year differences in carbon exchange at this site were small. In contrast, the modeled annual sums of CO2 exchange differed by a factor of two depending on wind direction. This indicated that the modeled time series captured the spatial variability in both the biogenic and anthropogenic CO2 sources and sinks in a reproducible way. The gap-filling approach developed here may also be useful for inhomogeneous sites other than urban areas, such as logged forests or ecosystems under disturbance from fire or pests.

Post-injection feasibility study with the reflectivity method for the Ketzin pilot site, Germany (CO2 storage in a saline aquifer)

NASA Astrophysics Data System (ADS)

Ivanova, Alexandra; Kempka, Thomas; Huang, Fei; Diersch [Gil], Magdalena; Lüth, Stefan

2016-04-01

3D time-lapse seismic surveys (4D seismic) have proven to be a suitable technique for monitoring of injected CO2, because when CO2 replaces brine as a free gas it considerably affects elastic properties of porous media. Forward modeling of a 4D seismic response to the CO2-fluid substitution in a storage reservoir is an inevitable step in such studies. At the Ketzin pilot site (CO2 storage) 67 kilotons of CO2 were injected into a saline aquifer between 2008 and 2013. In order to track migration of CO2 at Ketzin, 3D time-lapse seismic data were acquired by means of a baseline pre-injection survey in 2005 and 3 monitor surveys: in 2009, 2012 and in 2015 (the 1st post-injection survey). Results of the 4D seismic forward modeling with the reflectivity method suggest that effects of the injected CO2 on the 4D seismic data at Ketzin are significant regarding both seismic amplitudes and time delays. These results prove the corresponding observations in the real 4D seismic data at the Ketzin pilot site. But reservoir heterogeneity and seismic resolution, as well as random and coherent seismic noise are negative factors to be considered in this interpretation. Results of the 4D seismic forward modeling with the reflectivity method support the conclusion that even small amounts of injected CO2 can be monitored in such post-injected saline aquifer as the CO2 storage reservoir at the Ketzin pilot site both qualitatively and quantitatively with considerable uncertainties (Lüth et al., 2015). Reference: Lueth, S., Ivanova, A., Kempka, T. (2015): Conformity assessment of monitoring and simulation of CO2 storage: A case study from the Ketzin pilot site. - International Journal of Greenhouse Gas Control, 42, p. 329-339.

Re-assessment of plant carbon dynamics at the Duke free-air CO2 enrichment site: interactions of atmospheric [CO2] with nitrogen and water availability over stand development

Treesearch

Heather R. McCarthy; Ram Oren; Kurt H Johnsen; Anne Gallet-Budynek; Seth G. Pritchard; Charles W Cook; Shannon L. LaDeau; Robert B. Jackson; Adrien C. Finzi

2010-01-01

The potential for elevated [CO2]-induced changes to plant carbon (C) storage, through modifications in plant production and allocation of C among plant pools, is an important source of uncertainty when predicting future forest function. Utilizing 10 yr of data from the Duke free-air CO2 enrichment site, we evaluated the...

An Evaluation of Subsurface Microbial Activity Conditional to Subsurface Temperature, Porosity, and Permeability at North American Carbon Sequestration Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, B.; Mordensky, S.; Verba, Circe

Several nations, including the United States, recognize global climate change as a force transforming the global ecosphere. Carbon dioxide (CO 2) is a greenhouse gas that contributes to the evolving climate. Reduction of atmospheric CO 2 levels is a goal for many nations and carbon sequestration which traps CO 2 in the Earth’s subsurface is one method to reduce atmospheric CO 2 levels. Among the variables that must be considered in developing this technology to a national scale is microbial activity. Microbial activity or biomass can change rock permeability, alter artificial seals around boreholes, and play a key role inmore » biogeochemistry and accordingly may determine how CO 2 is sequestered underground. Certain physical parameters of a reservoir found in literature (e.g., temperature, porosity, and permeability) may indicate whether a reservoir can host microbial communities. In order to estimate which subsurface formations may host microbes, this report examines the subsurface temperature, porosity, and permeability of underground rock formations that have high potential to be targeted for CO 2 sequestration. Of the 268 North American wellbore locations from the National Carbon Sequestration Database (NATCARB; National Energy and Technology Laboratory, 2015) and 35 sites from Nelson and Kibler (2003), 96 sequestration sites contain temperature data. Of these 96 sites, 36 sites have temperatures that would be favorable for microbial survival, 48 sites have mixed conditions for supporting microbial populations, and 11 sites would appear to be unfavorable to support microbial populations. Future studies of microbe viability would benefit from a larger database with more formation parameters (e.g. mineralogy, structure, and groundwater chemistry), which would help to increase understanding of where CO 2 sequestration could be most efficiently implemented.« less

Tundra shrub effects on growing season energy and carbon dioxide exchange

NASA Astrophysics Data System (ADS)

Lafleur, Peter M.; Humphreys, Elyn R.

2018-05-01

Increased shrub cover on the Arctic tundra is expected to impact ecosystem-atmosphere exchanges of carbon and energy resulting in feedbacks to the climate system, yet few direct measurements of shrub tundra-atmosphere exchanges are available to corroborate expectations. Here we present energy and carbon dioxide (CO2) fluxes measured using the eddy covariance technique over six growing seasons at three closely located tundra sites in Canada’s Low Arctic. The sites are dominated by the tundra shrub Betula glandulosa, but percent cover varies from 17%–60% and average shrub height ranges from 18–59 cm among sites. The site with greatest percent cover and height had greater snow accumulation, but contrary to some expectations, it had similar late-winter albedo and snow melt dates compared to the other two sites. Immediately after snowmelt latent heat fluxes increased more slowly at this site compared to the others. Yet by the end of the growing season there was little difference in cumulative latent heat flux among the sites, suggesting evapotranspiration was not increased with greater shrub cover. In contrast, lower albedo and less soil thaw contributed to greater summer sensible heat flux at the site with greatest shrub cover, resulting in greater total atmospheric heating. Net ecosystem exchange of CO2 revealed the potential for enhanced carbon cycling rates under greater shrub cover. Spring CO2 emissions were greatest at the site with greatest percent cover of shrubs, as was summer net uptake of CO2. The seasonal net sink for CO2 was ~2 times larger at the site with the greatest shrub cover compared to the site with the least shrub cover. These results largely agree with expectations that the growing season feedback to the atmosphere arising from shrub expansion in the Arctic has the potential to be negative for CO2 fluxes but positive for turbulent energy fluxes.

[Direct Observation on the Temporal and Spatial Patterns of the CO2 Concentration in the Atmospheric of Nanjing Urban Canyon in Summer].

PubMed

Gao, Yun-qiu; Liu, Shou-dong; Hu, Ning; Wang, Shu-min; Deng, Li-chen; Yu, Zhou; Zhang, Zhen; Li, Xu-hui

2015-07-01

Direct observation of urban atmospheric CO2 concentration is vital for the research in the contribution of anthropogenic activity to the atmospheric abundance since cities are important CO2 sources. The observations of the atmospheric CO2 concentration at multiple sites/heights can help us learn more about the temporal and spatial patterns and influencing mechanisms. In this study, the CO2 concentration was observed at 5 sites (east, west, south, north and middle) in the main city area of Nanjing from July 18 to 25, 2014, and the vertical profile of atmospheric CO2 concentration was measured in the middle site at 3 heights (30 m, 65 m and 110 m). The results indicated that: (1) An obvious vertical CO2 gradient was found, with higher CO2 concentration [molar fraction of 427. 3 x 10(-6) (±18. 2 x 10(-6))] in the lower layer due to the strong influences of anthropogenic emissions, and lower CO2 concentration in the upper layers [411. 8 x 10(-6) (±15. 0 x 10(-6)) and 410. 9 x 10(-6) (±14. 6 x 10(-6)) at 65 and 110 m respectively] for the well-mixed condition. The CO2 concentration was higher and the vertical gradient was larger when the atmosphere was stable. (2) The spatial distribution pattern of CO2 concentration was dominated by wind and atmospheric stability. During the observation, the CO2 concentration in the southwest was higher than that in the northeast region with the CO2 concentration difference of 7. 8 x 10(-6), because the northwest wind was prevalent. And the CO2 concentration difference reduced with increasing wind speed since stronger wind diluted CO2 more efficiently. The more stable the atmosphere was, the higher the CO2 concentration was. (3) An obvious diurnal variation of CO2 concentration was shown in the 5 sites. A peak value occurred during the morning rush hours, the valley value occurred around 17:00 (Local time) and another high value occurred around 19:00 because of evening rush hour sometimes.

Complex doping of group 13 elements In and Ga in caged skutterudite CoSb 3

DOE PAGES

Xi, Lili; Qiu, Yting; Zheng, Shang; ...

2014-12-12

The complex doping behavior of Ga and In in CoSb 3 has been investigated using ab initio total-energy calculations and thermodynamics. The formation energies of void filling, Sb substitution and complex dual-site occupancy defects with different charge states, and their dependence on chemical potentials of species, were studied. Results show that Ga predominantly forms dual-site 2Ga VF–Ga Sb defects and substitutes for Sb only at very high Fermi levels or electron concentrations. In, on the other hand, can play multiple roles in skutterudites, including filling in the crystalline voids, substituting for Sb atoms or forming dual-site occupancy, among which themore » fully charge-compensated dual-site defects (2In VF–In Sb and 4In VF–2In Sb) are dominant. The equilibrium concentration ratio of impurities at void-filling sites to those at Sb-substitution sites for Ga-doped CoSb 3 is very close to be 2:1, while this value markedly deviates from 2:1 for In-doped CoSb 3. Furthermore, the 2:1 ratio of Ga doping in CoSb 3 leads to low electron concentration (~2 × 10 19 cm –3) and makes the doped system a semiconductor.« less

Allyl Fluorescein Ethers as Promising Fluorescent Probes for Carbon Monoxide Imaging in Living Cells.

PubMed

Feng, Shumin; Liu, Dandan; Feng, Weiyong; Feng, Guoqiang

2017-03-21

Recently, the fluorescent detection of carbon monoxide (CO) in living cells has attracted great attention. However, due to the lack of effective ways to construct fluorescent CO probes, fluorescent detection of CO in living cells is still in its infancy. In this paper, we report for the first time the use of allyl ether as a reaction site for construction of fluorescent CO probes. By this way, two readily available allyl fluorescein ethers were prepared, which were found to be highly selective and sensitive probes for CO in the presence of PdCl 2 . These probes have the merits of good stability, good water-solubility, and rapid and distinct colorimetric and remarkable fluorescent turn-on signal changes. Moreover, a very low dose of these two probes can be used to detect and track CO in living cells, indicating that these two probes could be very promising biological tools for CO detection in living systems. Overall, this work provided not only two new promising fluorescent CO probes but also a new way to devise fluorescent CO probes.