Exclusive Ni-N4 Sites Realize Near-Unity CO Selectivity for Electrochemical CO2 Reduction.

PubMed

Li, Xiaogang; Bi, Wentuan; Chen, Minglong; Sun, Yuexiang; Ju, Huanxin; Yan, Wensheng; Zhu, Junfa; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-10-25

Electrochemical reduction of carbon dioxide (CO 2 ) to value-added carbon products is a promising approach to reduce CO 2 levels and mitigate the energy crisis. However, poor product selectivity is still a major obstacle to the development of CO 2 reduction. Here we demonstrate exclusive Ni-N 4 sites through a topo-chemical transformation strategy, bringing unprecedentedly high activity and selectivity for CO 2 reduction. Topo-chemical transformation by carbon layer coating successfully ensures preservation of the Ni-N 4 structure to a maximum extent and avoids the agglomeration of Ni atoms to particles, providing abundant active sites for the catalytic reaction. The Ni-N 4 structure exhibits excellent activity for electrochemical reduction of CO 2 with particularly high selectivity, achieving high faradaic efficiency over 90% for CO in the potential range from -0.5 to -0.9 V and gives a maximum faradaic efficiency of 99% at -0.81 V with a current density of 28.6 mA cm -2 . We anticipate exclusive catalytic sites will shed new light on the design of high-efficiency electrocatalysts for CO 2 reduction.

Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)

DOE PAGES

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

2015-12-30

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO 2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C 1 pathway proceeds through COH to CHOH to form CH 4 whilemore » C 2 (C 3) pathways are kinetically blocked; (2) at neutral pH, the C 1 and C 2 (C 3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C 1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.« less

Assessment of Energy Efficiency Improvement and CO2 Emission Reduction Potentials in India's Cement Industry

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

Morrow, III, William R.; Hasanbeigi, Ali; Xu, Tengfang

2012-12-03

India’s cement industry is the second largest in the world behind China with annual cement production of 168 Mt in 2010 which accounted for slightly greater than six percent of the world’s annual cement production in the same year. To produce that amount of cement, the industry consumed roughly 700 PJ of fuel and 14.7 TWh of electricity. We identified and analyzed 22 energy efficiency technologies and measures applicable to the processes in the Indian cement industry. The Conservation Supply Curve (CSC) used in this study is an analytical tool that captures both the engineering and the economic perspectives ofmore » energy conservation. Using a bottom-up electricity CSC model and compared to an electricity price forecast the cumulative cost-effective plant-level electricity savings potential for the Indian cement industry for 2010- 2030 is estimated to be 83 TWh, and the cumulative plant-level technical electricity saving potential is 89 TWh during the same period. The grid-level CO2 emissions reduction associated with cost-effective electricity savings is 82 Mt CO2 and the electric grid-level CO2 emission reduction associated with technical electricity saving potential is 88 Mt CO2. Compared to a fuel price forecast, an estimated cumulative cost-effective fuel savings potential of 1,029 PJ with associated CO2 emission reduction of 97 Mt CO2 during 2010-2030 is possible. In addition, a sensitivity analysis with respect to the discount rate used is conducted to assess the effect of changes in this parameter on the results. The result of this study gives a comprehensive and easy to understand perspective to the Indian cement industry and policy makers about the energy efficiency potential and its associated cost over the next twenty years.« less

Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

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

Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

PubMed

Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

2017-11-01

Climate change, caused by heavy CO 2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO 2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO 2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO 2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO 2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO 2 reduction. In order to achieve high selectivity for CO 2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO 2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How do leaf hydraulics limit stomatal conductance at high water vapour pressure deficits?

PubMed

Bunce, James A

2006-08-01

A reduction in leaf stomatal conductance (g) with increasing leaf-to-air difference in water vapour pressure (D) is nearly ubiquitous. Ecological comparisons of sensitivity have led to the hypothesis that the reduction in g with increasing D serves to maintain leaf water potentials above those that would cause loss of hydraulic conductance. A reduction in leaf water potential is commonly hypothesized to cause stomatal closure at high D. The importance of these particular hydraulic factors was tested by exposing Abutilon theophrasti, Glycine max, Gossypium hirsutum and Xanthium strumarium to D high enough to reduce g and then decreasing ambient carbon dioxide concentration ([CO2]), and observing the resulting changes in g, transpiration rate and leaf water potential, and their reversibility. Reducing the [CO2] at high D increased g and transpiration rate and lowered leaf water potential. The abnormally high transpiration rates did not result in reductions in hydraulic conductance. Results indicate that low water potential effects on g at high D could be overcome by low [CO2], and that even lower leaf water potentials did not cause a reduction in hydraulic conductance in these well-watered plants. Reduced g at high D in these species resulted primarily from increased stomatal sensitivity to [CO2] at high D, and this increased sensitivity may mediate stomatal responses to leaf hydraulics at high D.

Selectivity of photoelectrochemical CO2 reduction modulated with electron transfer from size-tunable quantized energy states of CdSe nanocrystals

NASA Astrophysics Data System (ADS)

Cho, Hyunjin; Kim, Whi Dong; Lee, Kangha; Lee, Seokwon; Kang, Gil-Seong; Joh, Han-Ik; Lee, Doh C.

2018-01-01

We investigate the product selectivity of CO2 reduction using NiO photocathodes decorated with CdSe quantum dots (QDs) of varying size in a photoelectrochemical (PEC) cell. Size-tunable and quantized energy states of conduction band in CdSe QDs enable systematic control of electron transfer kinetics from CdSe QDs to NiO. It turns out that different size of CdSe QDs results in variation in product selectivity for CO2 reduction. The energy gap between conduction band edge and redox potential of each reduction product (e.g., CO and CH4) correlates with their production rate. The size dependence of the electron transfer rate estimated from the energy gap is in agreement with the selectivity of CO2 reduction products for all reduction products but CO. The deviation in the case of CO is attributed to sequential conversion of CO into CH4 with CO adsorbed on electrode surface. Based on a premise that the CdSe QDs would exhibit similar surface configuration regardless of QD size, it is concluded that the electron transfer kinetics proves to alter the selectivity of CO2 reduction.

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

Clouston, Laura J.; Bernales, Varinia; Carlson, Rebecca K.

Expanding a family of cobalt bimetallic complexes, we report the synthesis of the Ti(III) metalloligand, Ti[N(o-(NCH2P(iPr)2)C6H4)3] (abbreviated as TiL), and three heterobimetallics that pair cobalt with an early transition metal ion: CoTiL (1), K(crypt-222)[(N2)CoVL] (2), and K(crypt-222)[(N2)CoCrL] (3). The latter two complexes, along with previously reported K(crypt-222)[(N2)CoAlL] and K(crypt-222)[(N2)Co2L], constitute an isostructural series of cobalt bimetallics that bind dinitrogen in an end-on fashion, i.e. [(N2)CoML]-. The characterization of 1–3 includes cyclic voltammetry, X-ray crystallography, and infrared spectroscopy. The [CoTiL]0/– reduction potential is extremely negative at -3.20 V versus Fc+/Fc. In the CoML series where M is a transition metal, themore » reduction potentials shift anodically as M is varied across the first-row period. Among the [(N2)CoML]- compounds, the dinitrogen ligand is weakly activated, as evidenced by N–N bond lengths between 1.110(8) and 1.135(4) Å and by N–N stretching frequencies between 1971 and 1995 cm–1. Though changes in νN2 are subtle, the extent of N2 activation decreases across the first-row period. A correlation is found between the [CoML]0/– reduction potentials and N2 activation, where the more cathodic potentials correspond to lower N–N frequencies. Theoretical calculations of the [(N2)CoML]- complexes reveal important variations in the electronic structure and Co–M interactions, which depend on the exact nature of the supporting metal ion, M.« less

Effect of Leaf Water Potential on Internal Humidity and CO 2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

DOE PAGES

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia; ...

2017-02-06

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flatmore » surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Here, our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. Lastly, the omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.« less

Effect of Leaf Water Potential on Internal Humidity and CO 2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

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

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flatmore » surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Here, our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. Lastly, the omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.« less

Effect of Leaf Water Potential on Internal Humidity and CO2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

PubMed Central

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia; Salmon, Yann; Nikinmaa, Eero; Hari, Pertti; Hölttä, Teemu

2017-01-01

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Our results indicate that the reduction in vapor pressures of water and CO2 could enhance plant water use efficiency up to about 10% at a leaf water potential of −2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. The omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups. PMID:28220128

Effect of Leaf Water Potential on Internal Humidity and CO2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure.

PubMed

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia; Salmon, Yann; Nikinmaa, Eero; Hari, Pertti; Hölttä, Teemu

2017-01-01

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2 , thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. The omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.

Electrocatalytic reduction of carbon dioxide on electrodeposited tin-based surfaces

NASA Astrophysics Data System (ADS)

Alba, Bianca Christina S.; Camayang, John Carl A.; Mopon, Marlon L.; del Rosario, Julie Anne D.

2017-08-01

The electrocatalytic reduction of carbon dioxide to small organic molecular compounds provides a means of generating alternative fuel source while suppressing climate change. Suitable catalysts, however, are necessary to optimize its reaction kinetics towards more valuable products. Consequently, in this study, electrodeposited Sn electrodes have been developed as catalysts for CO2 electroreduction. Deposition potential was varied to produce different Sn catalysts. SEM showed varying morphologies and increasing amount as the applied potential becomes more negative. Cyclic voltammetry and chronoamperometry showed that the activity and stability of the catalysts towards CO2 reduction depend on the morphology and presence of tin oxides. These results provide a better understanding on the performance of electrodeposited Sn-based surfaces as catalysts for CO2 reduction.

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

NASA Technical Reports Server (NTRS)

Zhang, Bo; Harb, John N.; Davis, Robert C.; Kim, Jae-Woo; Chu, Sang-Hyon; Choi, Sang; Miller, Tim; Watt, Gerald D.

2004-01-01

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

CO2 Reduction: From the Electrochemical to Photochemical Approach

PubMed Central

Wu, Jinghua; Huang, Yang; Ye, Wen

2017-01-01

Abstract Increasing CO2 concentration in the atmosphere is believed to have a profound impact on the global climate. To reverse the impact would necessitate not only curbing the reliance on fossil fuels but also developing effective strategies capture and utilize CO2 from the atmosphere. Among several available strategies, CO2 reduction via the electrochemical or photochemical approach is particularly attractive since the required energy input can be potentially supplied from renewable sources such as solar energy. In this Review, an overview on these two different but inherently connected approaches is provided and recent progress on the development, engineering, and understanding of CO2 reduction electrocatalysts and photocatalysts is summarized. First, the basic principles that govern electrocatalytic or photocatalytic CO2 reduction and their important performance metrics are discussed. Then, a detailed discussion on different CO2 reduction electrocatalysts and photocatalysts as well as their generally designing strategies is provided. At the end of this Review, perspectives on the opportunities and possible directions for future development of this field are presented. PMID:29201614

How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

PubMed

Bachmeier, Andreas; Wang, Vincent C C; Woolerton, Thomas W; Bell, Sophie; Fontecilla-Camps, Juan C; Can, Mehmet; Ragsdale, Stephen W; Chaudhary, Yatendra S; Armstrong, Fraser A

2013-10-09

The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

China's Pathways to Achieving 40% ~ 45% Reduction in CO{sub 2} Emissions per Unit of GDP in 2020: Sectoral Outlook and Assessment of Savings Potential

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

Zheng, Nina; Fridley, David; Zhou, Nan

2011-09-30

Achieving China’s goal of reducing its carbon intensity (CO{sub 2} per unit of GDP) by 40% to 45% percent below 2005 levels by 2020 will require the strengthening and expansion of energy efficiency policies across the buildings, industries and transport sectors. This study uses a bottom-up, end-use model and two scenarios -- an enhanced energy efficiency (E3) scenario and an alternative maximum technically feasible energy efficiency improvement (Max Tech) scenario – to evaluate what policies and technical improvements are needed to achieve the 2020 carbon intensity reduction target. The findings from this study show that a determined approach by Chinamore » can lead to the achievement of its 2020 goal. In particular, with full success in deepening its energy efficiency policies and programs but following the same general approach used during the 11th Five Year Plan, it is possible to achieve 49% reduction in CO{sub 2} emissions per unit of GDP (CO{sub 2} emissions intensity) in 2020 from 2005 levels (E3 case). Under the more optimistic but feasible assumptions of development and penetration of advanced energy efficiency technology (Max Tech case), China could achieve a 56% reduction in CO{sub 2} emissions intensity in 2020 relative to 2005 with cumulative reduction of energy use by 2700 Mtce and of CO{sub 2} emissions of 8107 Mt CO{sub 2} between 2010 and 2020. Energy savings and CO{sub 2} mitigation potential varies by sector but most of the energy savings potential is found in energy-intensive industry. At the same time, electricity savings and the associated emissions reduction are magnified by increasing renewable generation and improving coal generation efficiency, underscoring the dual importance of end-use efficiency improvements and power sector decarbonization.« less

Interaction of Water Supply and N in Wheat 1

PubMed Central

Morgan, Jack A.

1984-01-01

The purpose of this study was to investigate effects of N nutrition and water stress on stomatal behavior and CO2 exchange rate in wheat (Triticum aestivum L. cv Olaf). Wheat plants were grown hydroponically with high (100 milligrams per liter) and low (10 milligrams per liter) N. When plants were 38 days old, a 24-day water stress cycle was begun. A gradual increase in nutrient solution osmotic pressure from 0.03 to 1.95 mega Pascals was achieved by incremental additions of PEG-6,000. Plants in both N treatments adjusted osmotically, although leaf water potential was consistently lower and relative water content greater for low N plants in the first half of the stress cycle. Leaf conductance of high N plants appeared greater than that of low N plants at high water potentials, but showed greater sensitivity to reductions in water potential as indicated by earlier stomatal closure during the stress cycle. The apparent greater stomatal sensitivity of high N plants was associated with a curvilinear relationship between leaf conductance and leaf water potential; low N plants exhibited more of a threshold response. Trends in [CO2]INT throughout the stress cycle indicated nonstomatal effects of water stress on CO2 exchange rate were greater in high N plants. Although estimates of [CO2]INT were generally lower in high N plants, they were relatively insensitive to leaf water potential-induced changes in leaf conductance. In contrast, [CO2]INT of low N plants dropped concomitantly with leaf conductance at low leaf water potentials. Oxygen response of CO2 exchange rate for both treatments was affected less by reductions in water potential than was CO2 exchange rate at 2.5% O2, suggesting that CO2 assimilation capacity of the leaves was affected more by reductions in leaf water potential than were processes related to photorespiration. PMID:16663780

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

PubMed Central

Reda, Torsten; Plugge, Caroline M.; Abram, Nerilie J.; Hirst, Judy

2008-01-01

Carbon dioxide (CO2) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO2 is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO2 from the atmosphere. However, available methods for the electrochemical reduction of CO2 require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO2 to formate. Electrocatalysis by FDH1 is thermodynamically reversible—only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO2 reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO2 reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO2 to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications. PMID:18667702

Redox-dependent complex formation by an ATP-dependent activator of the corrinoid/iron-sulfur protein

PubMed Central

Hennig, Sandra E.; Jeoung, Jae-Hun; Goetzl, Sebastian; Dobbek, Holger

2012-01-01

Movement, cell division, protein biosynthesis, electron transfer against an electrochemical gradient, and many more processes depend on energy conversions coupled to the hydrolysis of ATP. The reduction of metal sites with low reduction potentials (E0′ < -500 mV) is possible by connecting an energetical uphill electron transfer with the hydrolysis of ATP. The corrinoid-iron/sulfur protein (CoFeSP) operates within the reductive acetyl-CoA pathway by transferring a methyl group from methyltetrahydrofolate bound to a methyltransferase to the [Ni-Ni-Fe4S4] cluster of acetyl-CoA synthase. Methylation of CoFeSP only occurs in the low-potential Co(I) state, which can be sporadically oxidized to the inactive Co(II) state, making its reductive reactivation necessary. Here we show that an open-reading frame proximal to the structural genes of CoFeSP encodes an ATP-dependent reductive activator of CoFeSP. Our biochemical and structural analysis uncovers a unique type of reductive activator distinct from the electron-transferring ATPases found to reduce the MoFe-nitrogenase and 2-hydroxyacyl-CoA dehydratases. The CoFeSP activator contains an ASKHA domain (acetate and sugar kinases, Hsp70, and actin) harboring the ATP-binding site, which is also present in the activator of 2-hydroxyacyl-CoA dehydratases and a ferredoxin-like [2Fe-2S] cluster domain acting as electron donor. Complex formation between CoFeSP and its activator depends on the oxidation state of CoFeSP, which provides evidence for a unique strategy to achieve unidirectional electron transfer between two redox proteins. PMID:22431597

The right place for the right job in the photovoltaic life cycle.

PubMed

Kawajiri, Kotaro; Genchi, Yutaka

2012-07-03

The potential for photovoltaic power generation (PV) to reduce primary energy consumption (PEC) and CO(2) emissions depends on the physical locations of each stage of its life cycle. When stages are optimally located, CO(2) emissions are reduced nearly ten times as much as when each stage is located in the country having the largest current market share. The usage stage contributes the most to reducing CO(2) emissions and PEC, and total CO(2) emissions actually increase when PV is installed in countries having small CO(2) emissions from electricity generation. Global maps of CO(2) reduction potential indicate that Botswana and Gobi in Mongolia are the optimal locations to install PV due to favorable conditions for PV power generation and high CO(2) emissions from current electricity generation. However, the small electricity demand in those countries limits the contribution to global CO(2) reduction. The type of PVs has a small but significant effect on life cycle PEC and CO(2) emissions.

Structural change as a key component for agricultural non-CO2 mitigation efforts.

PubMed

Frank, Stefan; Beach, Robert; Havlík, Petr; Valin, Hugo; Herrero, Mario; Mosnier, Aline; Hasegawa, Tomoko; Creason, Jared; Ragnauth, Shaun; Obersteiner, Michael

2018-03-13

Agriculture is the single largest source of anthropogenic non-carbon dioxide (non-CO 2 ) emissions. Reaching the climate target of the Paris Agreement will require significant emission reductions across sectors by 2030 and continued efforts thereafter. Here we show that the economic potential of non-CO 2 emissions reductions from agriculture is up to four times as high as previously estimated. In fact, we find that agriculture could achieve already at a carbon price of 25 $/tCO 2 eq non-CO 2 reductions of around 1 GtCO 2 eq/year by 2030 mainly through the adoption of technical and structural mitigation options. At 100 $/tCO 2 eq agriculture could even provide non-CO 2 reductions of 2.6 GtCO 2 eq/year in 2050 including demand side efforts. Immediate action to favor the widespread adoption of technical options in developed countries together with productivity increases through structural changes in developing countries is needed to move agriculture on track with a 2 °C climate stabilization pathway.

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

Detection of CO2•- in the Electrochemical Reduction of Carbon Dioxide in N,N-Dimethylformamide by Scanning Electrochemical Microscopy.

PubMed

Kai, Tianhan; Zhou, Min; Duan, Zhiyao; Henkelman, Graeme A; Bard, Allen J

2017-12-27

The electrocatalytic reduction of CO 2 has been studied extensively and produces a number of products. The initial reaction in the CO 2 reduction is often taken to be the 1e formation of the radical anion, CO 2 •- . However, the electrochemical detection and characterization of CO 2 •- is challenging because of the short lifetime of CO 2 •- , which can dimerize and react with proton donors and even mild oxidants. Here, we report the generation and quantitative determination of CO 2 •- in N,N-dimethylformamide (DMF) with the tip generation/substrate collection (TG/SC) mode of scanning electrochemical microscopy (SECM). CO 2 was reduced at a hemisphere-shaped Hg/Pt ultramicroelectrode (UME) or a Hg/Au film UME, which were utilized as the SECM tips. The CO 2 •- produced can either dimerize to form oxalate within the nanogap between SECM tip and substrate or collected at SECM substrate (e.g., an Au UME). The collection efficiency (CE) for CO 2 •- depends on the distance (d) between the tip and substrate. The dimerization rate (6.0 × 10 8 M -1 s -1 ) and half-life (10 ns) of CO 2 •- can be evaluated by fitting the collection efficiency vs distance curve. The dimerized species of CO 2 •- , oxalate, can also be determined quantitatively. Furthermore, the formal potential (E 0 ') and heterogeneous rate constant (k 0 ) for CO 2 reduction were determined with different quaternary ammonium electrolytes. The significant difference in k 0 is due to a tunneling effect caused by the adsorption of the electrolytes on the electrode surface at negative potentials.

Selective electrochemical reduction of CO2 to CO with a cobalt chlorin complex adsorbed on multi-walled carbon nanotubes in water.

PubMed

Aoi, Shoko; Mase, Kentaro; Ohkubo, Kei; Fukuzumi, Shunichi

2015-06-25

Electrocatalytic reduction of CO2 occurred efficiently using a glassy carbon electrode modified with a cobalt(II) chlorin complex adsorbed on multi-walled carbon nanotubes at an applied potential of -1.1 V vs. NHE to yield CO with a Faradaic efficiency of 89% with hydrogen production accounting for the remaining 11% at pH 4.6.

Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

NASA Astrophysics Data System (ADS)

Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

2018-06-01

A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

PubMed

Guo, Sijie; Zhao, Siqi; Wu, Xiuqin; Li, Hao; Zhou, Yunjie; Zhu, Cheng; Yang, Nianjun; Jiang, Xin; Gao, Jin; Bai, Liang; Liu, Yang; Lifshitz, Yeshayahu; Lee, Shuit-Tong; Kang, Zhenhui

2017-11-28

Syngas, a CO and H 2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO 2 and H + /H 2 O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C 3 N 4 composite (a CO 2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co 3 O 4 , MoS 2 , Au and Pt serve as the HER component. The Co 3 O 4 -CDots-C 3 N 4 electrocatalyst is found to be the most efficient among the combinations studied. The H 2 /CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H 2 . Insight into the mechanisms balancing between CO 2 reduction and H 2 evolution when applying the HER-CDots-C 3 N 4 catalyst concept is provided.

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.

Promotional effect of surface hydroxyls on electrochemical reduction of CO 2 over SnO x/Sn electrode

DOE PAGES

Cui, Chaonan; Han, Jinyu; Zhu, Xinli; ...

2016-01-16

In this study, tin oxide (SnO x) formation on tin-based electrode surfaces during CO 2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnO x in CO 2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnO x. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H 2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface.more » CO 2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO 3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H 2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H 2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO 2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of –0.20 V (RHE), lower than that for the latter (–0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnO x monolayer on the electrode under the operating conditions promotes CO 2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.« less

Co-control of local air pollutants and CO2 in the Chinese iron and steel industry.

PubMed

Mao, Xianqiang; Zeng, An; Hu, Tao; Zhou, Ji; Xing, Youkai; Liu, Shengqiang

2013-01-01

The present study proposes an integrated multipollutant cocontrol strategy framework in the context of the Chinese iron and steel industry. The unit cost of pollutant reduction (UCPR) was used to examine the cost-effectiveness of each emission reduction measure. The marginal abatement cost (MAC) curves for SO2, NOx, PM2.5, and CO2 were drawn based on the UCPR and the abatement potential. Air pollutant equivalence (APeq) captures the nature of the damage value-weights of various air pollutants and acts as uniformization multiple air pollutants index. Single pollutant abatement routes designed in accordance with the corresponding reduction targets revealed that the cocontrol strategy has promising potential. Moreover, with the same reduction cost limitations as the single pollutant abatement routes, the multipollutant cocontrol routes are able to obtain more desirable pollution reduction and health benefits. Co-control strategy generally shows cost-effective advantage over single-pollutant abatement strategy. The results are robust to changing parameters according to sensitivity analysis. Co-control strategy would be an important step to achieve energy/carbon intensity targets and pollution control targets in China. Though cocontrol strategy has got some traction in policy debates, there are barriers to integrate it into policy making in the near future in China.

Reforestation in a high-CO2 world -- Higher mitigation potential than expected, lower adaptation potential than hoped for

NASA Astrophysics Data System (ADS)

Sonntag, Sebastian; Pongratz, Julia; Reick, Christian H.; Schmidt, Hauke

2016-06-01

We assess the potential and possible consequences for the global climate of a strong reforestation scenario for this century. We perform model experiments using the Max Planck Institute Earth System Model (MPI-ESM), forced by fossil-fuel CO2 emissions according to the high-emission scenario Representative Concentration Pathway (RCP) 8.5, but using land use transitions according to RCP4.5, which assumes strong reforestation. Thereby, we isolate the land use change effects of the RCPs from those of other anthropogenic forcings. We find that by 2100 atmospheric CO2 is reduced by 85 ppm in the reforestation model experiment compared to the reference RCP8.5 model experiment. This reduction is higher than previous estimates and is due to increased forest cover in combination with climate and CO2 feedbacks. We find that reforestation leads to global annual mean temperatures being lower by 0.27 K in 2100. We find large annual mean warming reductions in sparsely populated areas, whereas reductions in temperature extremes are also large in densely populated areas.

Preferentially Oriented Ag Nanocrystals with Extremely High Activity and Faradaic Efficiency for CO2 Electrochemical Reduction to CO.

PubMed

Peng, Xiong; Karakalos, Stavros G; Mustain, William E

2018-01-17

Selective electrochemical reduction of CO 2 is one of the most important processes to study because of its promise to convert this greenhouse gas to value-added chemicals at low cost. In this work, a simple anodization treatment was devised that first oxidizes Ag to Ag 2 CO 3 , then uses rapid electrochemical reduction to create preferentially oriented nanoparticles (PONs) of metallic Ag (PON-Ag) with high surface area as well as high activity and very high selectivity for the reduction of CO 2 to CO. The PON-Ag catalyst was dominated by (110) and (100) orientation, which allowed PON-Ag to achieve a CO Faradaic efficiency of 96.7% at an operating potential of -0.69 V vs RHE. This performance is not only significantly higher than that of polycrystalline Ag (60% at -0.87 V vs RHE) but also represents one of the best combinations of activity and selectivity achieved to date - all with a very simple, scalable approach to electrode fabrication.

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.

Abiotic CO2 reduction during geologic carbon sequestration facilitated by Fe(II)-bearing minerals

NASA Astrophysics Data System (ADS)

Nielsen, L. C.; Maher, K.; Bird, D. K.; Brown, G. E.; Thomas, B.; Johnson, N. C.; Rosenbauer, R. J.

2012-12-01

Redox reactions involving subsurface minerals and fluids and can lead to the abiotic generation of hydrocarbons from CO2 under certain conditions. Depleted oil reservoirs and saline aquifers targeted for geologic carbon sequestration (GCS) can contain significant quantities of minerals such as ferrous chlorite, which could facilitate the abiotic reduction of carbon dioxide to n-carboxylic acids, hydrocarbons, and amorphous carbon (C0). If such reactions occur, the injection of supercritical CO2 (scCO2) could significantly alter the oxidation state of the reservoir and cause extensive reorganization of the stable mineral assemblage via dissolution and reprecipitation reactions. Naturally occurring iron oxide minerals such as magnetite are known to catalyze CO2 reduction, resulting in the synthesis of organic compounds. Magnetite is thermodynamically stable in Fe(II) chlorite-bearing mineral assemblages typical of some reservoir formations. Thermodynamic calculations demonstrate that GCS reservoirs buffered by the chlorite-kaolinite-carbonate(siderite/magnesite)-quartz assemblage favor the reduction of CO2 to n-carboxylic acids, hydrocarbons, and C0, although the extent of abiotic CO2 reduction may be kinetically limited. To investigate the rates of abiotic CO2 reduction in the presence of magnetite, we performed batch abiotic CO2 reduction experiments using a Dickson-type rocking hydrothermal apparatus at temperatures (373 K) and pressures (100 bar) within the range of conditions relevant to GCS. Blank experiments containing CO2 and H2 were used to rule out the possibility of catalytic activity of the experimental apparatus. Reaction of brine-suspended magnetite nanoparticles with scCO2 at H2 partial pressures typical of reservoir rocks - up to 100 and 0.1 bars respectively - was used to investigate the kinetics of magnetite-catalyzed abiotic CO2 reduction. Later experiments introducing ferrous chlorite (ripidolite) were carried out to determine the potential for heterogeneous catalysis in GCS systems.

Hydricity, electrochemistry, and excited-state chemistry of Ir complexes for CO 2 reduction

DOE PAGES

Manbeck, Gerald F.; Garg, Komal; Shimoda, Tomoe; ...

2016-12-01

Here, we prepared electron-rich derivatives of [Ir(tpy)(ppy)Cl] + with modification of the bidentate (ppy) or tridentate (tpy) ligands in attempt to increase the reactivity for CO 2 reduction and the ability to transfer hydrides (hydricity). Density functional theory (DFT) calculations reveal that complexes with dimethyl-substituted ppy have similar hydricities to the non-substituted parent complex, and photocatalytic CO 2 reduction studies show selective CO formation. Substitution of tpy for bis(benzimidazole)-phenyl or -pyridine (L3 and L4, respectively) induces changes in the physical properties much more pronounced than addition of methyl groups to ppy. Theoretical data predict [Ir(L3)(ppy)(H)] is the strongest hydride donormore » among complexes studied in this work, but [Ir(L3)(ppy)(NCCH 3)] + cannot be reduced photochemically because the excited state reduction potential is only 0.52 V due to the negative ground state potential of –1.91 V. The excited state [Ir(L4)(ppy)(NCCH 3)] 2+ is the strongest oxidant among complexes studied in this work and the singly reduced species is formed readily upon photolysis in the presence of tertiary amines. Both [Ir(L3)(ppy)(NCCH 3)] + and [Ir(L4)(ppy)(NCCH 3)] 2+ exhibit electrocatalytic current for CO 2 reduction. While a significantly greater overpotential is needed for the L3 complex, a small amount of formate (5-10 %) generation in addition to CO was observed as predicted by the DFT calculations.« less

Activation of formylmethanofuran synthesis in cell extracts of Methanobacterium thermoautotrophicum.

PubMed Central

Bobik, T A; Wolfe, R S

1989-01-01

In cell extracts of Methanobacterium thermoautotrophicum, formylmethanofuran (formyl-MFR) synthesis (an essential CO2 fixation reaction that is an early step in CO2 reduction to methane) is subject to a complex activation that involves a heterodisulfide of coenzyme M and N-(7-mercaptoheptanoyl)threonine O3-phosphate (CoM-S-S-HTP). In this paper we report that titanium(III) citrate, a low-potential reducing agent, stimulated CO2 reduction to methane and activated formyl-MFR synthesis in cell extracts. Titanium(III) citrate functioned as the sole source of electrons for formyl-MFR synthesis and enabled this reaction to occur independently of CoM-S-S-HTP. In addition, CoM-S-S-HTP was found to activate an unknown electron carrier that reduced metronidazole. The activation of formyl-MFR synthesis by CoM-S-S-HTP may involve the activation of a low-potential electron carrier. PMID:2921239

Energetic valorization of wood waste: estimation of the reduction in CO2 emissions.

PubMed

Vanneste, J; Van Gerven, T; Vander Putten, E; Van der Bruggen, B; Helsen, L

2011-09-01

This paper investigates the potential CO(2) emission reductions related to a partial switch from fossil fuel-based heat and electricity generation to renewable wood waste-based systems in Flanders. The results show that valorization in large-scale CHP (combined heat and power) systems and co-firing in coal plants have the largest CO(2) reduction per TJ wood waste. However, at current co-firing rates of 10%, the CO(2) reduction per GWh of electricity that can be achieved by co-firing in coal plants is five times lower than the CO(2) reduction per GWh of large-scale CHP. Moreover, analysis of the effect of government support for co-firing of wood waste in coal-fired power plants on the marginal costs of electricity generation plants reveals that the effect of the European Emission Trading Scheme (EU ETS) is effectively counterbalanced. This is due to the fact that biomass integrated gasification combined cycles (BIGCC) are not yet commercially available. An increase of the fraction of coal-based electricity in the total electricity generation from 8 to 10% at the expense of the fraction of gas-based electricity due to the government support for co-firing wood waste, would compensate entirely for the CO(2) reduction by substitution of coal by wood waste. This clearly illustrates the possibility of a 'rebound' effect on the CO(2) reduction due to government support for co-combustion of wood waste in an electricity generation system with large installed capacity of coal- and gas-based power plants, such as the Belgian one. Copyright © 2011 Elsevier B.V. All rights reserved.

Advances in Photocatalytic CO2 Reduction with Water: A Review

PubMed Central

Nahar, Samsun; Zain, M. F. M.; Kadhum, Abdul Amir H.; Hasan, Hassimi Abu; Hasan, Md. Riad

2017-01-01

In recent years, the increasing level of CO2 in the atmosphere has not only contributed to global warming but has also triggered considerable interest in photocatalytic reduction of CO2. The reduction of CO2 with H2O using sunlight is an innovative way to solve the current growing environmental challenges. This paper reviews the basic principles of photocatalysis and photocatalytic CO2 reduction, discusses the measures of the photocatalytic efficiency and summarizes current advances in the exploration of this technology using different types of semiconductor photocatalysts, such as TiO2 and modified TiO2, layered-perovskite Ag/ALa4Ti4O15 (A = Ca, Ba, Sr), ferroelectric LiNbO3, and plasmonic photocatalysts. Visible light harvesting, novel plasmonic photocatalysts offer potential solutions for some of the main drawbacks in this reduction process. Effective plasmonic photocatalysts that have shown reduction activities towards CO2 with H2O are highlighted here. Although this technology is still at an embryonic stage, further studies with standard theoretical and comprehensive format are suggested to develop photocatalysts with high production rates and selectivity. Based on the collected results, the immense prospects and opportunities that exist in this technique are also reviewed here. PMID:28772988

Application of gas diffusion biocathode in microbial electrosynthesis from carbon dioxide.

PubMed

Bajracharya, Suman; Vanbroekhoven, Karolien; Buisman, Cees J N; Pant, Deepak; Strik, David P B T B

2016-11-01

Microbial catalysis of carbon dioxide (CO 2 ) reduction to multi-carbon compounds at the cathode is a highly attractive application of microbial electrosynthesis (MES). The microbes reduce CO 2 by either taking the electrons or reducing the equivalents produced at the cathode. While using gaseous CO 2 as the carbon source, the biological reduction process depends on the dissolution and mass transfer of CO 2 in the electrolyte. In order to deal with this issue, a gas diffusion electrode (GDE) was investigated by feeding CO 2 through the GDE into the MES reactor for its reduction at the biocathode. A combination of the catalyst layer (porous activated carbon and Teflon binder) and the hydrophobic gas diffusion layer (GDL) creates a three-phase interface at the electrode. So, CO 2 and reducing equivalents will be available to the biocatalyst on the cathode surface. An enriched inoculum consisting of acetogenic bacteria, prepared from an anaerobic sludge, was used as a biocatalyst. The cathode potential was maintained at -1.1 V vs Ag/AgCl to facilitate direct and/or hydrogen-mediated CO 2 reduction. Bioelectrochemical CO 2 reduction mainly produced acetate but also extended the products to ethanol and butyrate. Average acetate production rates of 32 and 61 mg/L/day, respectively, with 20 and 80 % CO 2 gas mixture feed were achieved with 10 cm 2 of GDE. The maximum acetate production rate remained 238 mg/L/day for 20 % CO 2 gas mixture. In conclusion, a gas diffusion biocathode supported bioelectrochemical CO 2 reduction with enhanced mass transfer rate at continuous supply of gaseous CO 2 . Graphical abstract ᅟ.

Novel RuCoSe as non-platinum catalysts for oxygen reduction reaction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Rozenfeld, Shmuel; Schechter, Michal; Teller, Hanan; Cahan, Rivka; Schechter, Alex

2017-09-01

Microbial electrochemical cells (MECs) are explored for the conversion of acetate directly to electrical energy. This device utilizes a Geobacter sulfurreducens anode and a novel RuCoSe air cathode. RuCoSe synthesized in selected compositions by a borohydride reduction method produces amorphous structures of powdered agglomerates. Oxygen reduction reaction (ORR) was measured in a phosphate buffer solution pH 7 using a rotating disc electrode (RDE), from which the kinetic current (ik) was measured as a function of potential and composition. The results show that ik of RuxCoySe catalysts increases in the range of XRu = 0.25 > x > 0.7 and y < 0.15 for all tested potentials. A poisoning study of RuCoSe and Pt catalysts in a high concentration acetate solution shows improved tolerance of RuCoSe to this fuel at acetate concentration ≥500 mM. MEC discharge plots under physiological conditions show that ∼ RuCo2Se (sample S3) has a peak power density of 750 mW cm-2 which is comparable with Pt 900 mW cm-2.

Reduction behavior and kinetics of vanadium-titanium sinters under high potential oxygen enriched pulverized coal injection

NASA Astrophysics Data System (ADS)

Ma, Jin-fang; Wang, Guang-wei; Zhang, Jian-liang; Li, Xin-yu; Liu, Zheng-jian; Jiao, Ke-xin; Guo, Jian

2017-05-01

In this work, the reduction behavior of vanadium-titanium sinters was studied under five different sets of conditions of pulverized coal injection with oxygen enrichment. The modified random pore model was established to analyze the reduction kinetics. The results show that the reduction rate of sinters was accelerated by an increase of CO and H2 contents. Meanwhile, with the increase in CO and H2 contents, the increasing range of the medium reduction index (MRE) of sinters decreased. The increasing oxygen enrichment ratio played a diminishing role in improving the reduction behavior of the sinters. The reducing process kinetic parameters were solved using the modified random role model. The results indicated that, with increasing oxygen enrichment, the contents of CO and H2 in the reducing gas increased. The reduction activation energy of the sinters decreased to between 20.4 and 23.2 kJ/mol.

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

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

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO 2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C 1 pathway proceeds through COH to CHOH to form CH 4 whilemore » C 2 (C 3) pathways are kinetically blocked; (2) at neutral pH, the C 1 and C 2 (C 3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C 1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.« less

Ag-doped Co3O4 catalyst derived from heterometallic MOF for syngas production by electrocatalytic reduction of CO2 in water

NASA Astrophysics Data System (ADS)

Zhang, Shi-Yuan; Yang, Yuan-Yuan; Zheng, Yue-Qing; Zhu, Hong-Lin

2018-07-01

Electrocatalytic reduction of CO2 to useful fuels or chemicals is a promising path for carbon recycling. In this study, a novel mixed-metallic MOF [Ag4Co2(pyz)PDC4][Ag2Co(pyz)2PDC2] was synthesized, and it transformed into Ag doped Co3O4 catalyst, which exhibits excellent electro-catalytic performance for reduction of CO2 in water to syngas (H2 + CO). The as-prepared Ag/Co3O4 material exhibits a high selectivity of CO in 0.1 M KHCO3 aqueous solution (CO2 saturated) with the corresponding faradaic efficiency up to 55.6%. Compared with the Ag/Co3O4 electrode, the maximum faradaic efficiency (FE) of CO of pure Co3O4 is 21.3% at - 1.8 V vs. SCE. The results show that the presence of Ag can improve the efficiency of CO significantly, thereby inhibiting the production of H2. The stability of the samples can be maintained for more than 10 h at - 1.8 V vs. SCE. The ratio of production between H2 and CO can be controlled by varying the potential values.

Faraday efficiency and mechanism of electrochemical surface reactions: CO2 reduction and H2 formation on Pt(111).

PubMed

Hussain, Javed; Jónsson, Hannes; Skúlason, Egill

2016-12-22

An atomic scale model of the electrical double layer is used to calculate the mechanism and rate of electrochemical reduction of CO 2 as well as H 2 formation at a Pt(111) electrode. The water layer contains solvated protons and the electrode has excess electrons at the surface. Density functional theory within the generalized gradient approximation is used to describe the electronic structure while the mechanism and activation energy of the various elementary reactions is obtained by calculating minimum energy paths using the nudged elastic band method. The applied electrical potential is deduced from the calculated work function. The optimal reaction mechanism for CO 2 reduction to either methane or methanol is found and the estimated rate compared with that of the competing reaction, H 2 formation. When the free energy of only the intermediates and reactants is taken into account, not the activation energy, Pt(111) would seem to be a good electrocatalyst for CO 2 reduction, significantly better than Cu(111). This, however, contradicts experimental findings. Detailed calculations reported here show that the activation energy for CO 2 reduction is high for both Heyrovsky and Tafel mechanisms on Pt(111) in the relevant range of applied potential. The rate-limiting step of the Heyrovsky mechanism, *COOH + H + + e - → *CO + H 2 O, is estimated to have an activation energy of 0.95 eV at -0.9 V vs. standard hydrogen electrode. Under the same conditions, the activation energy for H 2 formation is estimated to be only 0.5 eV. This explains why attempts to reduce CO 2 using platinum electrodes have produced only H 2 . A comparison is made with analogous results for Cu(111) [J. Hussain et al., Procedia Comput. Sci., 2015, 51, 1865] where a reaction mechanism with low activation energy for CO 2 electroreduction to methane was identified. The difference between the two electrocatalysts is discussed.

Carbon Dioxide Reduction Technology Trade Study

NASA Technical Reports Server (NTRS)

Jeng, Frank F.; Anderson, Molly S.; Abney, Morgan B.

2011-01-01

For long-term human missions, a closed-loop atmosphere revitalization system (ARS) is essential to minimize consumables. A carbon dioxide (CO2) reduction technology is used to reclaim oxygen (O2) from metabolic CO2 and is vital to reduce the delivery mass of metabolic O2. A key step in closing the loop for ARS will include a proper CO2 reduction subsystem that is reliable and with low equivalent system mass (ESM). Sabatier and Bosch CO2 reduction are two traditional CO2 reduction subsystems (CRS). Although a Sabatier CRS has been delivered to International Space Station (ISS) and is an important step toward closing the ISS ARS loop, it recovers only 50% of the available O2 in CO2. A Bosch CRS is able to reclaim all O2 in CO2. However, due to continuous carbon deposition on the catalyst surface, the penalties of replacing spent catalysts and reactors and crew time in a Bosch CRS are significant. Recently, technologies have been developed for recovering hydrogen (H2) from Sabatier-product methane (CH4). These include methane pyrolysis using a microwave plasma, catalytic thermal pyrolysis of CH4 and thermal pyrolysis of CH4. Further, development in Sabatier reactor designs based on microchannel and microlith technology could open up opportunities in reducing system mass and enhancing system control. Improvements in Bosch CRS conversion have also been reported. In addition, co-electrolysis of steam and CO2 is a new technology that integrates oxygen generation and CO2 reduction functions in a single system. A co-electrolysis unit followed by either a Sabatier or a carbon formation reactor based on Bosch chemistry could improve the overall competitiveness of an integrated O2 generation and CO2 reduction subsystem. This study evaluates all these CO2 reduction technologies, conducts water mass balances for required external supply of water for 1-, 5- and 10-yr missions, evaluates mass, volume, power, cooling and resupply requirements of various technologies. A system analysis and comparison among the technologies was made based on ESM, technology readiness level and reliability. Those technologies with potential were recommended for development.

Options to reduce greenhouse gas emissions during wastewater treatment for agricultural use.

PubMed

Fine, Pinchas; Hadas, Efrat

2012-02-01

Treatment of primarily-domestic sewage wastewater involves on-site greenhouse gas (GHG) emissions due to energy inputs, organic matter degradation and biological nutrient removal (BNR). BNR causes both direct emissions and loss of fertilizer value, thus eliminating possible reduction of emissions caused by fertilizer manufacture. In this study, we estimated on-site GHG emissions under different treatment scenarios, and present options for emission reduction by changing treatment methods, avoiding BNR and by recovering energy from biogas. Given a typical Israeli wastewater strength (1050mg CODl(-1)), the direct on-site GHG emissions due to energy use were estimated at 1618 and 2102g CO(2)-eq m(-3), respectively, at intermediate and tertiary treatment levels. A potential reduction of approximately 23-55% in GHG emissions could be achieved by fertilizer preservation and VS conversion to biogas. Wastewater fertilizers constituted a GHG abatement potential of 342g CO(2)-eq m(-3). The residual component that remained in the wastewater effluent following intermediate (oxidation ponds) and enhanced (mechanical-biological) treatments was 304-254g CO(2)-eq m(-3) and 65-34g CO(2)-eq m(-3), respectively. Raw sludge constituted approximately 47% of the overall wastewater fertilizers load with an abatement potential of 150g CO(2)-eq m(-3) (385kg CO(2)-eq dry tonne(-1)). Inasmuch as anaerobic digestion reduced it to 63g CO(2)-eq m(-3) (261kg CO(2)-eq dry tonne(-1)), the GHG abatement gained through renewable biogas energy (approx. 428g CO(2)-eq m(-3)) favored digestion. However, sludge composting reduced the fertilizer value to 17g CO(2)-eq m(-3) (121kg CO(2)-eq dry tonne(-1)) or less (if emissions, off-site inputs and actual phytoavailability were considered). Taking Israel as an example, fully exploiting the wastewater derived GHG abatement potential could reduce the State overall GHG emissions by almost 1%. This demonstrates the possibility of optional carbon credits which might be exploited in the construction of new wastewater treatment facilities, especially in developing countries. Copyright © 2011 Elsevier B.V. All rights reserved.

An Assessment of NASA Aeropropulsion Technologies: A System Study

NASA Technical Reports Server (NTRS)

Tong, Michael T.; Jones, Scott M.; Haller, William J.

2007-01-01

Aviation industry s robust growth rate has given rise to growing concerns about the contribution that aviation emissions will make to local air quality and global climate change. Over the last several years, NASA has been engaged in the development of aeropropulsion technologies with specific objectives to reduce aircraft emissions. A system analysis was performed to evaluate the potential impact of these propulsion technologies on aircraft CO2 (directly proportional to fuel burn) and NOx reductions. A large subsonic aircraft, with two 396-kN thrust (85,000-pound) engines was chosen for the study. Performance benefit estimates are presented for each technology, with a summary of potential emissions reduction possible from the development of these technologies. The results show that NASA s aeropropulsion technologies have the potential to significantly reduce the CO2 and NO(x) emissions. The results are used to support informed decision-making on the development of aeropropulsion technology portfolio for CO2 and NO(x) reductions.

Homogeneous Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide by Ni(cyclam)

NASA Astrophysics Data System (ADS)

Froehlich, Jesse Dan

The homogeneous electrochemical reduction of CO2 by the molecular catalyst [Ni(cyclam)]2+ was studied by electrochemistry and infrared spectroelectrochemistry. This catalyst has been previously shown to have increased CO2 reduction activity when adsorbed on a mercury electrode. The homogeneous reactivity, without a mercury electrode, was often ignored in the literature. Ni(cyclam) was found to efficiently and selectively produce CO at moderate overpotentials in both aqueous and mixed organic solvent systems in a homogenous fashion at an inert glassy carbon electrode. Methylated analogs of Ni(cyclam) were also studied and observed to have more positive reduction potentials and attenuated CO2 reduction activity. The electrochemical kinetics were probed by varying CO2 substrate and proton concentrations. Products of CO2 reduction are observed in infrared spectra obtained from spectroelectrochemical experiments. The two major species observed were a Ni(I) carbonyl, [Ni(cyclam)(CO)]+, and a Ni(II) coordinated bicarbonate, [Ni(cyclam)(CO2OH)] +. The rate-limiting step during electrocatalysis was determined to be CO loss from the deactivated species, [Ni(cyclam)(CO)]+, to produce the active catalyst, [Ni(cyclam)]+. Another macrocyclic complex, [Ni(TMC)]+, was deployed as a CO scavenger in order to inhibit the deactivation of [Ni(cyclam)] + by CO. Addition of the CO scavenger was shown to dramatically increase the catalytic current observed for CO2 reduction by [Ni(cyclam)] +. Evidence for the [Ni(TMC)]+ acting as a CO scavenger includes the observation of [Ni(TMC)(CO)]+ by IR. Density functional theory calculations, probing the optimized geometry of the [Ni(cyclam)(CO)] + species, are also presented. These findings have implications on the increased activity for CO2 reduction when [Ni(cyclam)] + is adsorbed on a mercury electrode. The [Ni(cyclam)(CO)] + structure has significant distortion of the Ni center out of the plane of the cyclam nitrogens. This distortion strengthens the Ni-CO interaction by increasing back-bonding interactions. This leads to the hypothesis that the mercury surface, through Hg-Ni interactions, prevents the distorted geometry seen in solution leading to a more planar geometry. This helps to destabilize the carbonyl adduct which inhibits the extent of CO poisoning of the catalyst when adsorbed on a mercury electrode. Alternative approaches to prevent CO poisoning without using such a toxic substance as mercury are critical to improving this unique catalytic system.

Reduced graphene oxide supported gold nanoparticles for electrocatalytic reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Saquib, Mohammad; Halder, Aditi

2018-02-01

Electrochemical reduction of carbon dioxide is one of the methods which have the capability to recycle CO2 into valuable products for energy and industrial applications. This research article describes about a new electrocatalyst "reduced graphene oxide supported gold nanoparticles" for selective electrochemical conversion of carbon dioxide to carbon monoxide. The main aim for conversion of CO2 to CO lies in the fact that the latter is an important component of syn gas (a mixture of hydrogen and carbon monoxide), which is then converted into liquid fuel via well-known industrial process called Fischer-Tropsch process. In this work, we have synthesized different composites of the gold nanoparticles supported on defective reduced graphene oxide to evaluate the catalytic activity of reduced graphene oxide (RGO)-supported gold nanoparticles and the role of defective RGO support towards the electrochemical reduction of CO2. Electrochemical and impedance measurements demonstrate that higher concentration of gold nanoparticles on the graphene support led to remarkable decrease in the onset potential of 240 mV and increase in the current density for CO2 reduction. Lower impedance and Tafel slope values also clearly support our findings for the better performance of RGOAu than bare Au for CO2 reduction.

Potential for reducing air-pollutants while achieving 2 °C global temperature change limit target.

PubMed

Hanaoka, Tatsuya; Akashi, Osamu; Fujiwara, Kazuya; Motoki, Yuko; Hibino, Go

2014-12-01

This study analyzes the potential to reduce air pollutants while achieving the 2 °C global temperature change limit target above pre-industrial levels, by using the bottom-up optimization model, AIM/Enduse[Global]. This study focuses on; 1) estimating mitigation potentials and costs for achieving 2 °C, 2.5 °C, and 3 °C target scenarios, 2) assessing co-benefits of reducing air pollutants such as NOx, SO2, BC, PM, and 3) analyzing features of sectoral attributions in Annex I and Non-Annex I groups of countries. The carbon tax scenario at 50 US$/tCO2-eq in 2050 can reduce GHG emissions more than the 3 °C target scenario, but a higher carbon price around 400 US$/tCO2-eq in 2050 is required to achieve the 2 °C target scenario. However, there is also a co-benefit of large reduction potential of air pollutants, in the range of 60-80% reductions in 2050 from the reference scenario while achieving the 2 °C target. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Ni III(OMe)]-mediated reductive activation of CO 2 affording a Ni(κ 1-OCO) complex

DOE PAGES

Chiou, Tzung -Wen; Tseng, Yen -Ming; Lu, Tsai -Te; ...

2016-02-24

Here, carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C 1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO 2, i.e. insertion of CO 2 producing bicarbonate/acetate/formate, cleavage of CO 2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO 2 affording CO/HCOOH/CH 3OH/CH 4/C 2H 4/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO 2 by the [Ni III(OMe)(P(C 6H 3-3-SiMe 3-2-S) 3)] – complex, yielding the [Ni III(κ 1-OCO˙ –)(P(C 6H 3-3-SiMe 3-2-S) 3)] – complex. The formationmore » of this unusual Ni III(κ 1-OCO ˙–) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [Ni III(SPh)], [Ni II(CO)], and [Ni II(N 2H 4)] toward CO 2, in contrast, demonstrates that the ionic [Ni III(OMe)] core attracts the binding of weak σ-donor CO 2 and triggers the subsequent reduction of CO 2 by the nucleophilic [OMe] – in the immediate vicinity. This metal–ligand cooperative activation of CO 2 may open a novel pathway promoting the subsequent incorporation of CO 2 in the buildup of functionalized products.« less

Assessment of Energy Efficiency Improvement in the United States Petroleum Refining Industry

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

Morrow, William R.; Marano, John; Sathaye, Jayant

2013-02-01

Adoption of efficient process technologies is an important approach to reducing CO 2 emissions, in particular those associated with combustion. In many cases, implementing energy efficiency measures is among the most cost-effective approaches that any refiner can take, improving productivity while reducing emissions. Therefore, careful analysis of the options and costs associated with efficiency measures is required to establish sound carbon policies addressing global climate change, and is the primary focus of LBNL’s current petroleum refining sector analysis for the U.S. Environmental Protection Agency. The analysis is aimed at identifying energy efficiency-related measures and developing energy abatement supply curves andmore » CO 2 emissions reduction potential for the U.S. refining industry. A refinery model has been developed for this purpose that is a notional aggregation of the U.S. petroleum refining sector. It consists of twelve processing units and account s for the additional energy requirements from steam generation, hydrogen production and water utilities required by each of the twelve processing units. The model is carbon and energy balanced such that crud e oil inputs and major refinery sector outputs (fuels) are benchmarked to 2010 data. Estimates of the current penetration for the identified energy efficiency measures benchmark the energy requirements to those reported in U.S. DOE 2010 data. The remaining energy efficiency potential for each of the measures is estimated and compared to U.S. DOE fuel prices resulting in estimates of cost- effective energy efficiency opportunities for each of the twelve major processes. A combined cost of conserved energy supply curve is also presented along with the CO 2 emissions abatement opportunities that exist in the U.S. petroleum refinery sector. Roughly 1,200 PJ per year of primary fuels savings and close to 500 GWh per y ear of electricity savings are potentially cost-effective given U.S. DOE fuel price forecasts. This represents roughly 70 million metric tonnes of CO 2 emission reductions assuming 2010 emissions factor for grid electricity. Energy efficiency measures resulting in an additional 400 PJ per year of primary fuels savings and close to 1,700 GWh per year of electricity savings, and an associated 24 million metric tonnes of CO 2 emission reductions are not cost-effective given the same assumption with respect to fuel prices and electricity emissions factors. Compared to the modeled energy requirements for the U.S. petroleum refining sector, the cost effective potential represents a 40% reduction in fuel consumption and a 2% reduction in electricity consumption. The non-cost-effective potential represents an additional 13% reduction in fuel consumption and an additional 7% reduction in electricity consumption. The relative energy reduction potentials are mu ch higher for fuel consumption than electricity consumption largely in part because fuel is the primary energy consumption type in the refineries. Moreover, many cost effective fuel savings measures would increase electricity consumption. The model also has the potential to be used to examine the costs and benefits of the other CO 2 mitigation options, such as combined heat and power (CHP), carbon capture, and the potential introduction of biomass feedstocks. However, these options are not addressed in this report as this report is focused on developing the modeling methodology and assessing fuels savings measures. These opportunities to further reduce refinery sector CO 2 emissions and are recommended for further research and analysis.« less

Sedimentary reservoir oxidation during geologic CO2 sequestration

NASA Astrophysics Data System (ADS)

Lammers, Laura N.; Brown, Gordon E.; Bird, Dennis K.; Thomas, Randal B.; Johnson, Natalie C.; Rosenbauer, Robert J.; Maher, Katharine

2015-04-01

Injection of carbon dioxide into subsurface geologic reservoirs during geologic carbon sequestration (GCS) introduces an oxidizing supercritical CO2 phase into a subsurface geologic environment that is typically reducing. The resulting redox disequilibrium provides the chemical potential for the reduction of CO2 to lower free energy organic species. However, redox reactions involving carbon typically require the presence of a catalyst. Iron oxide minerals, including magnetite, are known to catalyze oxidation and reduction reactions of C-bearing species. If the redox conditions in the reservoir are modified by redox transformations involving CO2, such changes could also affect mineral stability, leading to dissolution and precipitation reactions and alteration of the long-term fate of CO2 in GCS reservoirs. We present experimental evidence that reservoirs with reducing redox conditions are favorable environments for the relatively rapid abiotic reduction of CO2 to organic molecules. In these experiments, an aqueous suspension of magnetite nanoparticles was reacted with supercritical CO2 under pressure and temperature conditions relevant to GCS in sedimentary reservoirs (95-210 °C and ∼100 bars of CO2). Hydrogen production was observed in several experiments, likely caused by Fe(II) oxidation either at the surface of magnetite or in the aqueous phase. Heating of the Fe(II)-rich system resulted in elevated PH2 and conditions favorable for the reduction of CO2 to acetic acid. Implications of these results for the long-term fate of CO2 in field-scale systems were explored using reaction path modeling of CO2 injection into reservoirs containing Fe(II)-bearing primary silicate minerals, with kinetic parameters for CO2 reduction obtained experimentally. The results of these calculations suggest that the reaction of CO2 with reservoir constituents will occur in two primary stages (1) equilibration of CO2 with organic acids resulting in mineral-fluid disequilibrium, and (2) gradual dissolution of primary minerals promoting significant CO2 reduction through the release of Fe(II). The reduction of CO2 is identified as a new trapping mechanism that could significantly enhance the long-term stability of GCS reservoirs. Identification of reservoir characteristics that promote CO2 redox transformations could be used as an additional factor in screening geologic reservoirs for GCS.

Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction.

PubMed

Wang, Jing; Huang, Zhengqing; Liu, Wei; Chang, Chunran; Tang, Haolin; Li, Zhijun; Chen, Wenxing; Jia, Chunjiang; Yao, Tao; Wei, Shiqiang; Wu, Yuen; Li, Yadong

2017-12-06

We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E onset , 1.06 vs 1.03 V) and half-wave potential (E 1/2 , 0.863 vs 0.858 V) than commercial Pt/C. The fuel cell test reveals (Fe,Co)/N-C outperforms most reported Pt-free catalysts in H 2 /O 2 and H 2 /air. In addition, this cathode catalyst with dual metal sites is stable in a long-term operation with 50 000 cycles for electrode measurement and 100 h for H 2 /air single cell operation. Density functional theory calculations reveal the dual sites is favored for activation of O-O, crucial for four-electron oxygen reduction.

Carbon supported MnO2-CoFe2O4 with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Ying; Liu, Qing; Hu, Tianjun; Zhang, Limin; Deng, Youquan

2017-05-01

The catalyst MnO2-CoFe2O4/C was firstly synthesized via a two-step process and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The composite exhibits better bifunctional activity than CoFe2O4/C and MnO2/C. Moreover, superior durability and high methanol tolerance in alkaline media outperforms the commercial Pt/C electrocatalyst, which signifying its excellent potential for applications in metal-air batteries and alkaline fuel cells.

Preparation of Cu2O modified TiO2 nanopowder and its application to the visible light photoelectrocatalytic reduction of CO2 to CH3OH

NASA Astrophysics Data System (ADS)

Li, Bin; Niu, Wenchao; Cheng, Yongwei; Gu, Junjie; Ning, Ping; Guan, Qingqing

2018-05-01

Cu2O/TiO2 nanopowders were prepared and used as thin film electrode raw materials for CO2 photoelectroreduction. Characterization results from XRD, TEM, UV-Vis and BET show that Cu2O/TiO2 composites have regular morphology, narrow band gap, excellent textural properties, and exhibits marked response of visible light. The photoelectrocatalytic results show that CO2 can be reduced to formaldehyde (i.e., intermediate) and finally methanol (i.e., end product). In addition, the CO2 photoelectroreduction pathway and the mechanism of photoelectrocatalysis are discussed. In summary, the work reports a potential method of CO2 reduction by visible-light photocatalysis without an external bias.

Estimation of the composition of intermetallic compounds in LiCl-KCl molten salt by cyclic voltammetry.

PubMed

Liu, Ya L; Liu, Kui; Yuan, Li Y; Chai, Zhi F; Shi, Wei Q

2016-08-15

In this work, the compositions of Ce-Al, Er-Al and La-Bi intermetallic compounds were estimated by the cyclic voltammetry (CV) technique. At first, CV measurements were carried out at different reverse potentials to study the co-reduction processes of Ce-Al, Er-Al and La-Bi systems. The CV curves obtained were then re-plotted with the current as a function of time, and the coulomb number of each peak was calculated. By comparing the coulomb number of the related peaks, the compositions of the Ce-Al, Er-Al and La-Bi intermetallic compounds formed in the co-reduction process could be estimated. The results showed that Al11Ce3, Al3Ce, Al2Ce and AlCe could be formed by the co-reduction of Ce(iii) and Al(iii). For the co-reduction of Er(iii) and Al(iii), Al3Er2, Al2Er and AlEr were formed. In a La(iii) and Bi(iii) co-existing system in LiCl-KCl melts, LaBi2, LaBi and Li3Bi were the major products as a result of co-reduction.

Reconstructing metabolic pathways of a member of the genus Pelotomaculum suggesting its potential to oxidize benzene to carbon dioxide with direct reduction of sulfate.

PubMed

Dong, Xiyang; Dröge, Johannes; von Toerne, Christine; Marozava, Sviatlana; McHardy, Alice C; Meckenstock, Rainer U

2017-03-01

The enrichment culture BPL is able to degrade benzene with sulfate as electron acceptor and is dominated by an organism of the genus Pelotomaculum. Members of Pelotomaculum are usually known to be fermenters, undergoing syntrophy with anaerobic respiring microorganisms or methanogens. By using a metagenomic approach, we reconstructed a high-quality genome (∼2.97 Mbp, 99% completeness) for Pelotomaculum candidate BPL. The proteogenomic data suggested that (1) anaerobic benzene degradation was activated by a yet unknown mechanism for conversion of benzene to benzoyl-CoA; (2) the central benzoyl-CoA degradation pathway involved reductive dearomatization by a class II benzoyl-CoA reductase followed by hydrolytic ring cleavage and modified β-oxidation; (3) the oxidative acetyl-CoA pathway was utilized for complete oxidation to CO2. Interestingly, the genome of Pelotomaculum candidate BPL has all the genes for a complete sulfate reduction pathway including a similar electron transfer mechanism for dissimilatory sulfate reduction as in other Gram-positive sulfate-reducing bacteria. The proteome analysis revealed that the essential enzymes for sulfate reduction were all formed during growth with benzene. Thus, our data indicated that, besides its potential to anaerobically degrade benzene, Pelotomaculum candidate BPL is the first member of the genus that can perform sulfate reduction. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

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

Thoi, VanSara; Kornienko, Nick; Margarit, C

2013-06-07

The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity formore » the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.« less

Structural Dynamics and Evolution of Bismuth Electrodes during Electrochemical Reduction of CO 2 in Imidazolium-Based Ionic Liquid Solutions

DOE PAGES

Medina-Ramos, Jonnathan; Lee, Sang Soo; Fister, Timothy T.; ...

2017-09-12

Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO 2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM) and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM] +) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF 6 or TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi 2O 3) and metallic bismuth (Bi 0), and that the reduction of oxidized bismuth speciesmore » to Bi 0 is fully achieved under potentials at which CO 2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO 2 reduction near -1.75 V vs. Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM] + solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than -1.6 V vs. Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO 2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. By contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO 2 reduction. In conclusion, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM] + based electrolytes, including the reduction of bismuth oxide to bismuth metal, changes in roughness and near-surface viscosity.« less

A review on photocatalytic CO2 reduction using perovskite oxide nanomaterials

NASA Astrophysics Data System (ADS)

Zeng, Sheng; Kar, Piyush; Thakur, Ujwal Kumar; Shankar, Karthik

2018-02-01

As the search for efficient catalysts for CO2 photoreduction continues, nanostructured perovskite oxides have emerged as a class of high-performance photocatalytic materials. The perovskite oxide candidates for CO2 photoreduction are primarily nanostructured forms of titanates, niobates, tantalates and cobaltates. These materials form the focus of this review article because they are much sought-after due to their nontoxic nature, adequate chemical stability, and tunable crystal structures, bandgaps and surface energies. As compared to conventional semiconductors and nanomaterial catalysts, nanostructured perovskite oxides also exhibit an extended optical-absorption edge, longer charge carrier lifetimes, and favorable band-alignment with respect to reduction potential of activated CO2 and reduction products of the same. While CO2 reduction product yields of several hundred μmol-1 h-1 are observed with many types of perovskite oxide nanomaterials in stand-alone forms, yield of such quantities are not common with semiconductor nanomaterials of other types. In this review, we present current state-of-the-art synthesis methods to form perovskite oxide nanomaterials, and procedures to engineer their bandgaps. This review also presents a comprehensive summary and discussion on crystal structures, defect distribution, morphologies and electronic properties of the perovskite oxides, and correlation of these properties to CO2 photoreduction performance. This review offers researchers key insights for developing advanced perovskite oxides in order to further improve the yields of CO2 reduction products.

Mg-Doped CuFeO 2 Photocathodes for Photoelectrochemical Reduction of Carbon Dioxide

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

Gu, Jing; Wuttig, Anna; Krizan, Jason W.

2013-05-22

Mg-doped CuFeO 2 delafossite is reported to be photoelectrochemically active for CO 2 reduction. The material was prepared via conventional solid-state methods, and subsequently assembled into an electrode as a pressed pellet. Addition of a Mg 2+ dopant is found to substantially improve the conductivity of the material, with 0.05% Mg-doped CuFeO 2 electrodes displaying photocathodic currents under visible irradiation. Photocurrent is found to onset at irradiation wavelengths of ~800 nm with the incident photon-to-current efficiency reaching a value of 14% at 340 nm using an applied electrode potential of –0.4 V vs SCE. Photoelectrodes were determined to have amore » –1.1 V vs SCE conduction band edge and were found capable of the reduction of CO 2 to formate at 400 mV of underpotential. The conversion efficiency is maximized at –0.9 V vs SCE, with H 2 production contributing as a considerable side reaction. Lastly, these results highlight the potential to produce Mg-doped p-type metal oxide photocathodes with a band structure tuned to optimize CO 2 reduction.« less

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

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

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

DOE PAGES

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.; ...

2015-12-07

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

DOE PAGES

Wu, Yueshen; Jiang, Jianbing; Weng, Zhe; ...

2017-07-26

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO 2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO 2 reduction. Here in this paper, we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site –1 s –1 and a Faradaic efficiency as high as 95% for CO 2 electroreduction to CO at -1.7 V vs the standard hydrogen electrode in anmore » organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO 2. This represents the first example of a transition-metal complex for CO 2 electroreduction catalysis with its metal center being redox-innocent under working conditions.« less

Electroreduction of CO2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

PubMed Central

2017-01-01

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at −1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions. PMID:28852698

Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

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

Wu, Yueshen; Jiang, Jianbing; Weng, Zhe

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO 2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO 2 reduction. Here in this paper, we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site –1 s –1 and a Faradaic efficiency as high as 95% for CO 2 electroreduction to CO at -1.7 V vs the standard hydrogen electrode in anmore » organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO 2. This represents the first example of a transition-metal complex for CO 2 electroreduction catalysis with its metal center being redox-innocent under working conditions.« less

Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

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

Wu, Yueshen; Jiang, Jianbing; Weng, Zhe

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at -1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center ismore » critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions.« 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.

[Cobalt(III)-EDTA] - Reduction by Thermophilic Methanogen Methanothermobacter Thermautotrophicus

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

Singh, Rajesh; Dong, Hailiang; Liu, Deng

2015-06-30

Cobalt is a metal contaminant at high temperature radioactive waste disposal sites. In previous studies have largely focused on mesophilic microorganisms to remediate cobalt, despite the presence of thermophilic microorganisms at such sites. In this study,Methanothermobacter thermautotrophicus, a thermophilic methanogen, was used to reduce Co(III) in the form of [Co(III)–EDTA] -. Bioreduction experiments were conducted in a growth medium with H 2/CO 2 as a growth substrate at initial Co(III) concentrations of 1, 2, 4, 7, and 10 mM. At low Co(III) concentrations (< 4 mM), a complete reduction was observed within a week. Wet chemistry, X-ray absorption near-edge structuremore » (XANES) and electron paramagnetic resonance (EPR) analyses were all consistent in revealing the reduction kinetics. But, at higher concentrations (7 and 10 mM) the reduction extents only reached 69.8% and 48.5%, respectively, likely due to the toxic effect of Co(III) to the methanogen cells as evidenced by a decrease in total cellular protein at these Co(III) concentrations. Methanogenesis was inhibited by Co(III) bioreduction, possibly due to impaired cell growth and electron diversion from CO 2 to Co(III). Overall, our results demonstrated the ability of M. thermautotrophicus to reduce Co(III) to Co(II) and its potential application for remediating 60Co contaminant at high temperature subsurface radioactive waste disposal sites.« less

Novel Solvent System for Post Combustion CO{sub 2} Capture

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

Brown, Alfred; Brown, Nathan

2013-09-30

The purpose of this project was to evaluate the performance of ION’s lead solvent and determine if ION’s solvent candidate could potentially meet DOE’s target of achieving 90% CO{sub 2} Capture from a 550 MWe Pulverized Coal Plant without resulting in an increase in COE greater than 35%. In this project, ION’s lead solvent demonstrated a 65% reduction in regeneration energy and a simultaneous 35% reduction in liquid to gas ratio (L/G) in comparison to aqMEA at 90% CO{sub 2} capture using actual flue gas at 0.2 MWe. Results have clearly demonstrated that the ION technology is in line withmore » DOE performance expectations and has the potential to meet DOE’s performance targets in larger scale testing environments.« less

Perovskite nanocomposites as effective CO2-splitting agents in a cyclic redox scheme

PubMed Central

Zhang, Junshe; Haribal, Vasudev; Li, Fanxing

2017-01-01

We report iron-containing mixed-oxide nanocomposites as highly effective redox materials for thermochemical CO2 splitting and methane partial oxidation in a cyclic redox scheme, where methane was introduced as an oxygen “sink” to promote the reduction of the redox materials followed by reoxidation through CO2 splitting. Up to 96% syngas selectivity in the methane partial oxidation step and close to complete conversion of CO2 to CO in the CO2-splitting step were achieved at 900° to 980°C with good redox stability. The productivity and production rate of CO in the CO2-splitting step were about seven times higher than those in state-of-the-art solar-thermal CO2-splitting processes, which are carried out at significantly higher temperatures. The proposed approach can potentially be applied for acetic acid synthesis with up to 84% reduction in CO2 emission when compared to state-of-the-art processes. PMID:28875171

Response of anaerobic carbon cycling to water table manipulation in an Alaskan rich fen

USGS Publications Warehouse

Kane, E.S.; Chivers, M.R.; Turetsky, M.R.; Treat, C.C.; Petersen, D.G.; Waldrop, M.; Harden, J.W.; McGuire, A.D.

2013-01-01

To test the effects of altered hydrology on organic soil decomposition, we investigated CO2 and CH4 production potential of rich-fen peat (mean surface pH = 6.3) collected from a field water table manipulation experiment including control, raised and lowered water table treatments. Mean anaerobic CO2 production potential at 10 cm depth (14.1 ± 0.9 μmol C g−1 d−1) was as high as aerobic CO2 production potential (10.6 ± 1.5 μmol C g−1 d−1), while CH4 production was low (mean of 7.8 ± 1.5 nmol C g−1 d−1). Denitrification enzyme activity indicated a very high denitrification potential (197 ± 23 μg N g−1 d−1), but net NO-3 reduction suggested this was a relatively minor pathway for anaerobic CO2 production. Abundances of denitrifier genes (nirK and nosZ) did not change across water table treatments. SO2-4 reduction also did not appear to be an important pathway for anaerobic CO2 production. The net accumulation of acetate and formate as decomposition end products in the raised water table treatment suggested that fermentation was a significant pathway for carbon mineralization, even in the presence of NO-3. Dissolved organic carbon (DOC) concentrations were the strongest predictors of potential anaerobic and aerobic CO2 production. Across all water table treatments, the CO2:CH4 ratio increased with initial DOC leachate concentrations. While the field water table treatment did not have a significant effect on mean CO2 or CH4 production potential, the CO2:CH4 ratio was highest in shallow peat incubations from the drained treatment. These data suggest that with continued drying or with a more variable water table, anaerobic CO2 production may be favored over CH4 production in this rich fen. Future research examining the potential for dissolved organic substances to facilitate anaerobic respiration, or alternative redox processes that limit the effectiveness of organic acids as substrates in anaerobic metabolism, would help explain additional uncertainty concerning carbon mineralization in this system.

Mechanistic insights into electrochemical reduction of CO2 over Ag using density functional theory and transport models

PubMed Central

Goodpaster, Jason D.; Weber, Adam Z.

2017-01-01

Electrochemical reduction of CO2 using renewable sources of electrical energy holds promise for converting CO2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in the reaction. Moreover, cathode polarization can influence the kinetics of CO2 reduction. Here, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO2 that is consistent with experiments. Simulations based on this mechanism also describe the dependence of the H2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation. PMID:28973926

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

NASA Astrophysics Data System (ADS)

Liu, Min; Pang, Yuanjie; Zhang, Bo; de Luna, Phil; Voznyy, Oleksandr; Xu, Jixian; Zheng, Xueli; Dinh, Cao Thang; Fan, Fengjia; Cao, Changhong; de Arquer, F. Pelayo García; Safaei, Tina Saberi; Mepham, Adam; Klinkova, Anna; Kumacheva, Eugenia; Filleter, Tobin; Sinton, David; Kelley, Shana O.; Sargent, Edward H.

2016-09-01

Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

Mechanism of electrocatalytic hydrogen production by a di-iron model of iron-iron hydrogenase: a density functional theory study of proton dissociation constants and electrode reduction potentials.

PubMed

Surawatanawong, Panida; Tye, Jesse W; Darensbourg, Marcetta Y; Hall, Michael B

2010-03-28

Simple dinuclear iron dithiolates such as (mu-SCH2CH2CH2S)[Fe(CO)3]2, (1) and (mu-SCH2CH2S)[Fe(CO)3]2 (2) are functional models for diiron-hydrogenases, [FeFe]-H2ases, that catalyze the reduction of protons to H2. The mechanism of H2 production with 2 as the catalyst and with both toluenesulfonic (HOTs) and acetic (HOAc) acids as the H+ source in CH3CN solvent has been examined by density functional theory (DFT). Proton dissociation constants (pKa) and electrode reduction potentials (E(o)) are directly computed and compared to the measured pKa of HOTs and HOAc acids and the experimental reduction potentials. Computations show that when the strong acid, HOTs, is used as a proton source the one-electron reduced species 2- can be protonated to form a bridging hydride complex as the most stable structure. Then, this species can be reduced and protonated to form dihydrogen and regenerate 2. This cycle produces H2 via an ECEC process at an applied potential of -1.8 V vs. Fc/Fc+. A second faster process opens for this system when the species produced at the ECEC step above is further reduced and H2 release returns the system to 2- rather than 2, an E[CECE] process. On the other hand, when the weak acid, HOAc, is the proton source a more negative applied reduction potential (-2.2 V vs. Fc/Fc+) is necessary. At this potential two one-electron reductions yield the dianion 2(2-) before the first protonation, which in this case occurs on the thiolate. Subsequent reduction and protonation form dihydrogen and regenerate 2- through an E[ECEC] process.

Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation

DOE PAGES

Chen, Sheng-Yu; Song, Wenqiao; Lin, Hui-Jan; ...

2016-03-08

In this work, a generic one-pot hydrothermal synthesis route has been successfully designed and utilized to in situ grow uniform manganese oxide nanorods and nanowires onto the cordierite honeycomb monolithic substrates, forming a series of nanoarray-based monolithic catalysts. During the synthesis process, three types of potassium salt oxidants have been used with different reduction potentials, i.e., K 2Cr 2O 7, KClO 3, and K 2S 2O 8, denoted as HM-DCM, HM-PCR, and HM-PSF, respectively. The different reduction potentials of the manganese source (Mn 2+) and oxidants induced the formation of manganese oxide nanoarrays with different morphology, surface area, and reactivitymore » of carbon monoxide (CO) oxidation. K 2Cr 2O 7 and KClO 3 can induce sharp and long nanowires with slow growth rates due to their low reduction potentials. In comparison, the nanoarrays of HM-PSF presented shorter nanorods but displayed an efficient 90% CO oxidation conversion at 200 °C (T90) without noble-metal loading. Reducibility tests for the three monolithic catalysts by hydrogen temperature-programmed reduction revealed an activation energy order of HM-PSF > HM-DCM > HM-PCR for CO oxidation. The characterizations of oxygen temperature-programmed desorption and X-ray photoelectron spectroscopy indicated the abundant surface-adsorbed oxygen and lattice oxygen contributing to the superior reactivity of HM-PSF. Finally, the straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment.« less

Descriptors and Thermodynamic Limitations of Electrocatalytic Carbon Dioxide Reduction on Rutile Oxide Surfaces.

PubMed

Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine A

2016-11-23

A detailed understanding of the electrochemical reduction of CO 2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO 2 (1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO 2 reduction reaction (CO2RR) based on thermodynamic analysis. We aim to specify the requirements for CO2RR catalysts to establish adsorbate scaling relations and use these to derive activity volcanoes. Computational results show that the OH* binding free energy is a good descriptor of the thermodynamic limitations and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits their suitability. We determine the ideal binding free energy for H* and OH* to facilitate selective CO2RR over H 2 /CO evolution to be ΔG B [H]>0.5 eV and -0.5 eV<ΔG B [OH]<0.1 eV. The Re-containing overlayers considered in this work display excellent promise for selectivity, although they are active at a highly reducing potential. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analyzing and forecasting CO2 emission reduction in China's steel industry

NASA Astrophysics Data System (ADS)

Gao, Chengkang; Wang, Dan; Zhao, Baohua; Chen, Shan; Qin, Wei

2015-03-01

Recent measures of carbon dioxide emissions from the steel industry of China have indicated a high rate of total CO2 emissions from the industry, even compared to the rest of the world. So, CO2 emission reduction in China's steel industry was analyzed, coupling the whole process and scenarios analysis. First, assuming that all available advanced technologies are almost adopted, this study puts forward some key potential-sectors and explores an optimal technical route for reducing CO2 emissions from the Chinese steel industry based on whole process analysis. The results show that in the stages of coking, sintering, and iron making, greater potential for reducing emissions would be fulfilled by taking some technological measures. If only would above well-developed technologies be fulfill, the CO2 emissions from 5 industry production stages would be reduced substantially, and CO2 emissions per ton of steel could be decreased to 1.24 (ton/ton-steel) by 2020. At the same time, the scenarios analysis indicates that if mature carbon-reducing technologies are adopted, and if the difference between steel output growth rate and the GDP growth rate could be controlled below 3%, CO2 emissions from China's steel industry would approach the goal of reducing CO2 emissions per GDP unit by 40%-45% of the 2005 level by 2020. This indicates that the focus of carbon dioxide emissions reduction in China lies in policy adjustments in order to enhance technological application, and lies in reasonably controlling the pace of growth of GDP and steel output.

The chemical biology of methanogenesis

NASA Astrophysics Data System (ADS)

Ferry, James G.

2010-12-01

Two distinct pathways account for most of the CH 4 produced in the majority of the diverse and vast anaerobic environments of Earth's biosphere by microbes that are classified in the Archaea domain of life: conversion of the methyl group of acetate to CH 4 in the aceticlastic pathway and reduction of CO 2 with electrons derived from H 2, formate or CO in the CO 2 reduction pathway. Minor, albeit ecologically important, amounts of CH 4 are produced by conversion of methylotrophic substrates methanol, methylamines and methyl sulfides. Although all pathways have terminal steps in common, they deviate in the initial steps leading to CH 4 and mechanisms for synthesizing ATP for growth. Hydrogen gas is the major reductant for CO 2-reducing methanogens in the deep subsurface, although H 2 is also utilized by CO 2-reducing microbes from the Bacteria domain that produce acetate for the aceticlastic methanogens. This review presents fundamentals of the two major CH 4-producing pathways with a focus on understanding the potential for biologically-produced CH 4 on Mars.

Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction

PubMed Central

2017-01-01

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon–carbon coupled products via self-assembly of supramolecular cages at molecular–materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm2) at a potential of −0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation. PMID:28979945

Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction

DOE PAGES

Gong, Ming; Cao, Zhi; Liu, Wei; ...

2017-09-13

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO 2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here in this paper, we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon-carbon coupled products via self-assembly of supramolecular cages at molecular-materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm 2) at a potential ofmore » -0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.« less

Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes

DOE PAGES

Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.; ...

2017-06-22

Increases in energy demand and in chemical production, together with the rise in CO 2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO 2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO –) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO – production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO 2 tomore » HCOO – on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO –. Our results show that Sn electrodes produce HCOO –, carbon monoxide (CO), and hydrogen (H 2) across a range of potentials and that HCOO – production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO production on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO – production. Instead, *OCHO is suggested to be the key intermediate for the CO 2RR to HCOO – transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO –. Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO 2 reduction to HCOO – on metal surfaces.« less

Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes

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

Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.

Increases in energy demand and in chemical production, together with the rise in CO 2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO 2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO –) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO – production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO 2 tomore » HCOO – on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO –. Our results show that Sn electrodes produce HCOO –, carbon monoxide (CO), and hydrogen (H 2) across a range of potentials and that HCOO – production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO production on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO – production. Instead, *OCHO is suggested to be the key intermediate for the CO 2RR to HCOO – transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO –. Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO 2 reduction to HCOO – on metal surfaces.« less

Push or Pull? Proton Responsive Ligand Effects in Rhenium Tricarbonyl CO 2 Reduction Catalysts

DOE PAGES

Manbeck, Gerald F.; Muckerman, James T.; Szalda, David J.; ...

2015-02-19

Proton responsive ligands offer control of catalytic reactions through modulation of pH-dependent properties, second coordination sphere stabilization of transition states, or by providing a local proton source for multi-proton, multi-electron reactions. Two fac-[ReI(α-diimine)(CO)₃Cl] complexes with α-diimine = 4,4'- (or 6,6'-) dihydroxy-2,2'-bipyridine (4DHBP and 6DHBP) have been prepared and analyzed as electrocatalysts for reduction of carbon dioxide. Consecutive electrochemical reduction of these complexes yields species identical to those obtained by chemical deprotonation. An energetically feasible mechanism for reductive deprotonation is proposed in which the bpy anion is protonated followed by loss of H₂ and 2H⁺. Cyclic voltammetry reveals a two-electron, three-wavemore » system owing to competing EEC and ECE pathways. The chemical step of the ECE pathway might be attributed to the reductive deprotonation. but cannot be distinguished from chloride dissociation. The rate obtained by digital simulation is approximately 8 s⁻¹. Under CO₂, these competing reactions generate a two-slope catalytic waveform with onset potential of –1.65 V vs Ag/AgCl. Reduction of CO₂ to CO by the [ReI (4DHBP–2H⁺)(CO)₃]⁻ suggests the interaction of CO₂ with the deprotonated species or a third reduction followed by catalysis. Conversely, the reduced form of [Re(6DHBP)(CO)₃Cl] converts CO₂ to CO with a single turnover.« less

Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

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

Cui, Chaonan; Han, Jinyu; Zhu, Xinli

Tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react with the hydroxyl, formingmore » a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous C-O bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of -0.20 V (RHE), lower than that for the latter (-0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby, providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing Center of Tianjin University is acknowledged for providing services to the computing cluster. CC acknowledges the support of 24 China Scholarship Council (CSC). QG acknowledges the support of NSF-CBET program (Award no. CBET-1438440). DM was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington.« less

Anaerobic degradation of 2-aminobenzoic acid (anthranilic acid) via benzoyl-coenzyme A (CoA) and cyclohex-1-enecarboxyl-CoA in a denitrifying bacterium.

PubMed Central

Lochmeyer, C; Koch, J; Fuchs, G

1992-01-01

The enzymes catalyzing the initial reactions in the anaerobic degradation of 2-aminobenzoic acid (anthranilic acid) were studied with a denitrifying Pseudomonas sp. anaerobically grown with 2-aminobenzoate and nitrate as the sole carbon and energy sources. Cells grown on 2-aminobenzoate are simultaneously adapted to growth with benzoate, whereas cells grown on benzoate degrade 2-aminobenzoate several times less efficiently than benzoate. Evidence for a new reductive pathway of aromatic metabolism and for four enzymes catalyzing the initial steps is presented. The organism contains 2-aminobenzoate-coenzyme A ligase (2-aminobenzoate-CoA ligase), which forms 2-aminobenzoyl-CoA. 2-Aminobenzoyl-CoA is then reductively deaminated to benzoyl-CoA by an oxygen-sensitive enzyme, 2-aminobenzoyl-CoA reductase (deaminating), which requires a low potential reductant [Ti(III)]. The specific activity is 15 nmol of 2-aminobenzoyl-CoA reduced min-1 mg-1 of protein at an optimal pH of 7. The two enzymes are induced by the substrate under anaerobic conditions only. Benzoyl-CoA is further converted in vitro by reduction with Ti(III) to six products; the same products are formed when benzoyl-CoA or 2-aminobenzoyl-CoA is incubated under reducing conditions. Two of them were identified preliminarily. One product is cyclohex-1-enecarboxyl-CoA, the other is trans-2-hydroxycyclohexane-carboxyl-CoA. The complex transformation of benzoyl-CoA is ascribed to at least two enzymes, benzoyl-CoA reductase (aromatic ring reducing) and cyclohex-1-enecarboxyl-CoA hydratase. The reduction of benzoyl-CoA to alicyclic compounds is catalyzed by extracts from cells grown anaerobically on either 2-aminobenzoate or benzoate at almost the same rate (10 to 15 nmol min-1 mg-1 of protein). In contrast, extracts from cells grown anaerobically on acetate or grown aerobically on benzoate or 2-aminobenzoate are inactive. This suggests a sequential induction of the enzymes. Images PMID:1592816

Anaerobic degradation of 2-aminobenzoic acid (anthranilic acid) via benzoyl-coenzyme A (CoA) and cyclohex-1-enecarboxyl-CoA in a denitrifying bacterium.

PubMed

Lochmeyer, C; Koch, J; Fuchs, G

1992-06-01

The enzymes catalyzing the initial reactions in the anaerobic degradation of 2-aminobenzoic acid (anthranilic acid) were studied with a denitrifying Pseudomonas sp. anaerobically grown with 2-aminobenzoate and nitrate as the sole carbon and energy sources. Cells grown on 2-aminobenzoate are simultaneously adapted to growth with benzoate, whereas cells grown on benzoate degrade 2-aminobenzoate several times less efficiently than benzoate. Evidence for a new reductive pathway of aromatic metabolism and for four enzymes catalyzing the initial steps is presented. The organism contains 2-aminobenzoate-coenzyme A ligase (2-aminobenzoate-CoA ligase), which forms 2-aminobenzoyl-CoA. 2-Aminobenzoyl-CoA is then reductively deaminated to benzoyl-CoA by an oxygen-sensitive enzyme, 2-aminobenzoyl-CoA reductase (deaminating), which requires a low potential reductant [Ti(III)]. The specific activity is 15 nmol of 2-aminobenzoyl-CoA reduced min-1 mg-1 of protein at an optimal pH of 7. The two enzymes are induced by the substrate under anaerobic conditions only. Benzoyl-CoA is further converted in vitro by reduction with Ti(III) to six products; the same products are formed when benzoyl-CoA or 2-aminobenzoyl-CoA is incubated under reducing conditions. Two of them were identified preliminarily. One product is cyclohex-1-enecarboxyl-CoA, the other is trans-2-hydroxycyclohexane-carboxyl-CoA. The complex transformation of benzoyl-CoA is ascribed to at least two enzymes, benzoyl-CoA reductase (aromatic ring reducing) and cyclohex-1-enecarboxyl-CoA hydratase. The reduction of benzoyl-CoA to alicyclic compounds is catalyzed by extracts from cells grown anaerobically on either 2-aminobenzoate or benzoate at almost the same rate (10 to 15 nmol min-1 mg-1 of protein). In contrast, extracts from cells grown anaerobically on acetate or grown aerobically on benzoate or 2-aminobenzoate are inactive. This suggests a sequential induction of the enzymes.

The climate mitigation gap: education and government recommendations miss the most effective individual actions

NASA Astrophysics Data System (ADS)

Wynes, Seth; Nicholas, Kimberly A.

2017-07-01

Current anthropogenic climate change is the result of greenhouse gas accumulation in the atmosphere, which records the aggregation of billions of individual decisions. Here we consider a broad range of individual lifestyle choices and calculate their potential to reduce greenhouse gas emissions in developed countries, based on 148 scenarios from 39 sources. We recommend four widely applicable high-impact (i.e. low emissions) actions with the potential to contribute to systemic change and substantially reduce annual personal emissions: having one fewer child (an average for developed countries of 58.6 tonnes CO2-equivalent (tCO2e) emission reductions per year), living car-free (2.4 tCO2e saved per year), avoiding airplane travel (1.6 tCO2e saved per roundtrip transatlantic flight) and eating a plant-based diet (0.8 tCO2e saved per year). These actions have much greater potential to reduce emissions than commonly promoted strategies like comprehensive recycling (four times less effective than a plant-based diet) or changing household lightbulbs (eight times less). Though adolescents poised to establish lifelong patterns are an important target group for promoting high-impact actions, we find that ten high school science textbooks from Canada largely fail to mention these actions (they account for 4% of their recommended actions), instead focusing on incremental changes with much smaller potential emissions reductions. Government resources on climate change from the EU, USA, Canada, and Australia also focus recommendations on lower-impact actions. We conclude that there are opportunities to improve existing educational and communication structures to promote the most effective emission-reduction strategies and close this mitigation gap.

PdCo nanoparticles supported on carbon fibers derived from cotton: Maximum utilization of Pd atoms for efficient reduction of nitroarenes.

PubMed

Yang, Jin; Wang, Wei David; Dong, Zhengping

2018-08-15

In the present work, a facile and environment-friendly route is illustrated for the efficient fabrication of highly dispersed PdCo nanoparticles (NPs) by modified cotton-derived carbon fibers (PdCo/CCF). Firstly, commercial cotton was impregnated with CoCl 2 , followed by pyrolysis under high calcination temperature to obtain the Co NPs modified CCF sample (Co/CCF). Secondly, Co/CCF was treated with Pd(AcO) 2 aqueous solution, wherein, through a spontaneous replacement reaction process, Pd 2+ is reduced to metallic Pd and mostly covered on the surface of the Co NPs. Thus, the PdCo/CCF catalyst was obtained avoiding the use of toxic reductants like NaBH 4 , NH 2 NH 2 and HCHO. The PdCo/CCF catalyst exhibits excellent catalytic activity and recyclability for the reduction of 4-nitrophenol and other nitroarenes compared with Pd/CCF, PdCo NPs and many other noble metals based catalysts. The reasons could be attributed to the uniformly dispersed and accessible PdCo NPs on the surface of the CCF, and the Pd atoms deposited on the Co NPs surface that makes the Pd active sites available for optimum use. The PdCo/CCF catalyst also exhibits potential application for catalytic reduction of nitroarenes in a fixed bed reactor under mild reaction conditions. Furthermore, the PdCo/CCF catalyst can be magnetically recycled and reused for at least ten cycles without either losing catalytic activity or leaching of Pd active sites, thereby confirming its superior stability. Copyright © 2018 Elsevier Inc. All rights reserved.

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

Medina-Ramos, Jonnathan; Lee, Sang Soo; Fister, Timothy T.

Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO 2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM) and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM] +) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF 6 or TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi 2O 3) and metallic bismuth (Bi 0), and that the reduction of oxidized bismuth speciesmore » to Bi 0 is fully achieved under potentials at which CO 2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO 2 reduction near -1.75 V vs. Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM] + solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than -1.6 V vs. Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO 2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. By contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO 2 reduction. In conclusion, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM] + based electrolytes, including the reduction of bismuth oxide to bismuth metal, changes in roughness and near-surface viscosity.« less

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

Medina-Ramos, Jonnathan; Lee, Sang Soo; Fister, Timothy T.

Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved undermore » potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near -1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than -1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM]+-based electrolytes, including the reduction of bismuth oxide to bismuth metal and changes in roughness and near-surface viscosity.« less

Viability and metal reduction of Shewanella oneidensis MR-1 under CO2 stress: implications for ecological effects of CO2 leakage from geologic CO2 sequestration.

PubMed

Wu, Bing; Shao, Hongbo; Wang, Zhipeng; Hu, Yandi; Tang, Yinjie J; Jun, Young-Shin

2010-12-01

To study potential ecological impacts of CO(2) leakage to shallow groundwater and soil/sediments from geologic CO(2) sequestration (GCS) sites, this work investigated the viability and metal reduction of Shewanella oneidensis MR-1 under CO(2) stress. While MR-1 could grow under high-pressure nitrogen gas (500 psi), the mix of 1% CO(2) with N(2) at total pressures of 15 or 150 psi significantly suppressed the growth of MR-1, compared to the N(2) control. When CO(2) partial pressures were over 15 psi, the growth of MR-1 stopped. The reduced bacterial viability was consistent with the pH decrease and cellular membrane damage under high pressure CO(2). After exposure to 150 psi CO(2) for 5 h, no viable cells survived, the cellular contents were released, and microscopy images confirmed significant cell structure deformation. However, after a relatively short exposure (25 min) to 150 psi CO(2), MR-1 could fully recover their growth within 24 h after the stress was removed, and the reduction of MnO(2) by MR-1 was observed right after the stress was removed. Furthermore, MR-1 survived better if the cells were aggregated rather than suspended, or if pH buffering minerals, such as calcite, were present. To predict the cell viability under different CO(2) pressures and exposure times, a two-parameter mathematical model was developed.

Hybrid binuclear-cobalt-phthalocyanine as oxygen reduction reaction catalyst in single chamber microbial fuel cells

NASA Astrophysics Data System (ADS)

Li, Baitao; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

2014-12-01

A novel hybrid binuclear-cobalt-phthalocyanine (Bi-CoPc) is developed as the cathode catalyst to replace the costly platinum (Pt) in single chamber microbial fuel cells (SCMFCs). Bi-CoPc/C is integrated with metal oxides (NiO and CoO) to form macrocyclic complex for enhanced oxygen reduction rate (ORR). The characteristics of hybrid catalysts (Bi-CoPc/C-CoO and Bi-CoPc/C-NiO) are compared with Co-contained catalysts (CoPc/C and Bi-CoPc/C) and metal oxide catalysts (NiO and CoO). The increase in O and N functional groups indicates the benefits of NiO and CoO to the cathode catalysts. The cyclic voltammetry (CV) shows the reduction peak for Bi-CoPc/C-NiO and Bi-CoPc/C-CoO at -0.12 V and -0.22 V, respectively. The power densities (368 mW m-2 and 400 mW m-2) of SCMFCs with Bi-CoPc/C-CoO and Bi-CoPc-NiO/C are the highest among the cathodes tested, and close to that of Pt (450 mW m-2). This study demonstrates that hybrid Bi-CoPc/C with metal oxides has a great potential as a cost-effective catalyst in MFCs.

Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

1995-01-01

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles

PubMed Central

2016-01-01

Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure–activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from −0.3 V to −0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at −0.3 V. PMID:27163043

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2016-03-23

Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure-activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from -0.3 V to -0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at -0.3 V.

CoMn2O4-supported functionalized carbon nanotube: efficient catalyst for oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Nengwu; Lu, Yu; Liu, Bowen; Zhang, Taiping; Huang, Jianjian; Shi, Chaohong; Wu, Pingxiao; Dang, Zhi; Wang, Ruixin

2017-10-01

Recently, the synthesis of nonprecious metal catalysts with low cost and high oxygen reduction reaction (ORR) efficiency is paid much attention in field of microbial fuel cells (MFCs). Transition metal oxides (AMn2O4, A = Co、Ni, and Zn) supported on carbon materials such as graphene and carbon nanotube exhibit stronger electroconductivity and more active sites comparing to bare AMn2O4. Herein, we demonstrate an easy operating Hummer's method to functionalize carbon nanotubes (CNTs) with poly (diallyldimethylammonium chloride) in order to achieve effective loading of CoMn2O4 nanoparticles, named CoMn2O4/PDDA-CNTs (CMODT). After solvothermal treatment, nanoscale CoMn2O4 particles ( 80 nm) were successfully attached on the noncovalent functionalized carbon nanotube. Results show that such composites possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in neutral media. Electrochemical detections as cyclic voltammogram (CV) and rotating ring-disk electrode tests (RRDE) showed that the potential of oxygen reduction peak of 30% CMODT was at - 0.3 V (vs Ag/AgCl), onset potential was at + 0.4 V. Among them, 30% CMODT composite appeared the best candidate of oxygen reduction via 3.9 electron transfer pathway. When 30% CMODT composite was utilized as cathode catalyst in air cathode MFC, the reactor obtained 1020 mW m-2 of the highest maximum power density and 0.781 V of open circuit voltage. The excellent activity and low cost (0.2 g-1) of the hybrid materials demonstrate the potential of transition metal oxide/carbon as effective cathode ORR catalyst for microbial fuel cells. [Figure not available: see fulltext.

Correlation Analysis of Reactivity in the Photo- and Electro-Reduction of Cobalt(III) Complexes in Binary Organic Solvent/Water Mixtures

NASA Astrophysics Data System (ADS)

Sivaraj, Kumarasamy; Elango, Kuppanagounder P.

2008-08-01

The photo- and electro-reduction of a series of cobalt(III) complexes of the type cis-β - [Co(trien)(RC6H4NH2)Cl]Cl2 with R = H, p-OMe, p-OEt, p-Me, p-Et, p-F, and m-Me has been studied in binary propan-2-ol/water mixtures. The redox potential (E1/2) and photo-reduction quantum yield (ΦCo(II)) data were correlated with solvent and structural parameters with the aim to shed some light on the mechanism of these reactions. The correlation of E1/2 and ΦCo(II) with macroscopic solvent parameters, viz. relative permittivity, indicated that the reactivity is influenced by both specific and non-specific solute-solvent interactions. The Kamlet-Taft solvatochromic comparison method was used to separate and quantify these effects: An increase in the percentage of organic cosolvent in the medium enhances both reduction processes, and there exists a good linear correlation between E1/2 and ΦCo(II), suggesting a similar solvation of the participants in these redox processes.

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

DOE PAGES

Fields, Meredith; Hong, Xin; Norskov, Jens K.; ...

2018-06-12

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

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

Fields, Meredith; Hong, Xin; Norskov, Jens K.

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

Mechanistic insights into electrochemical reduction of CO 2 over Ag using density functional theory and transport models

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

Singh, Meenesh R.; Goodpaster, Jason D.; Weber, Adam Z.

Electrochemical reduction of CO 2 using renewable sources of electrical energy holds promise for converting CO 2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in themore » reaction. Moreover, cathode polarization can influence the kinetics of CO 2 reduction. Here in this work, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO 2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO 2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO 2 that is consistent with experiments. Additionally, simulations based on this mechanism also describe the dependence of the H 2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation.« less

Mechanistic insights into electrochemical reduction of CO 2 over Ag using density functional theory and transport models

DOE PAGES

Singh, Meenesh R.; Goodpaster, Jason D.; Weber, Adam Z.; ...

2017-10-02

Electrochemical reduction of CO 2 using renewable sources of electrical energy holds promise for converting CO 2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in themore » reaction. Moreover, cathode polarization can influence the kinetics of CO 2 reduction. Here in this work, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO 2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO 2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO 2 that is consistent with experiments. Additionally, simulations based on this mechanism also describe the dependence of the H 2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation.« less

Two novel Pb(II) coordination polymers (CPs) based on 4-(4-oxopyridin-1(4H)-yl) and 3-(4-oxopyridin-1(4H)-yl) phthalic acid: Band gaps, structures, and their photoelectrocatalytic properties in CO2-saturated system

NASA Astrophysics Data System (ADS)

Yan, Zhi Shuo; Long, Ji Ying; Gong, Yun; Lin, Jian Hua

2018-05-01

Based on 4-(4-oxopyridin-1(4H)-yl) phthalic acid (H2L1) and 3-(4-oxopyridin-1(4H)-yl) phthalic acid (H2L2), two novel Pb(II) coordination polymers (CPs) formulated as [Pb4Cl4·(L1)2·H2O]n (CP 1), [Pb3Cl4·L2·H2O]n (CP 2) were solvothermally synthesized and characterized by single-crystal X-ray diffraction. The two novel Pb(II) CPs (CPs 1 and 2) possessed different structures. Density functional theory (DFT) calculations revealed the two CPs had different band structures yet the characteristic of semiconductors in common. Their valence band (VB) and conduction band (CB) positions were determined by Mott-Schottky and UV-visible diffuse reflectance analyses. The photoelectrocatalytic performance of the two CPs towards CO2 reduction were tested by photocurrent responses at various applied potentials. And the E =-1.4 V vs SCE (-0.74 V vs NHE) was selected as the required potential according to the regulation of photocurrent responses at various tested potentials in CO2-saturated system. The photoelectrocatalytic performance of CP 2 was superior to that of CP 1 owing to the well-matched CB position of CP 2 and CO2 reduction potentials at the required potential of -1.4 V vs SCE (-0.74 V vs NHE). In addition, the photoelectrolytic experiment were performed 1 h in the CO2-saturated 0.2 M Na2SO4 solution at the required potential of -1.4 V vs SCE (-0.74 V vs NHE) with and without illumination, and we initially demonstrated the influence of visible light in the CO2-saturated photoelectrocatalytic measurement system and the reason of stability in 1 h chronoamperometry.

Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes

DOE PAGES

Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.; ...

2017-03-09

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO 2 reduction ability. We reported complexes are of the type Re(N-N)(CO) 3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO 2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO 2 reduction by 1 in acetonitrile using densitymore » functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG ‡ = 27.2 kcal mol –1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO) 3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (i cat/i p) 2, up to 7 times larger than that of I.« less

Potential of porous Co3O4 nanorods as cathode catalyst for oxygen reduction reaction in microbial fuel cells.

PubMed

Kumar, Ravinder; Singh, Lakhveer; Zularisam, A W; Hai, Faisal I

2016-11-01

This study aims to investigate the potential of porous Co3O4 nanorods as the cathode catalyst for oxygen reduction reaction (ORR) in aqueous air cathode microbial fuel cells (MFCs). The porous Co3O4 nanorods were synthesized by a facile and cost-effective hydrothermal method. Three different concentrations (0.5mg/cm(2), 1mg/cm(2), and 2mg/cm(2)) of Co3O4 nanorods coated on graphite electrodes were used to test its performance in MFCs. The results showed that the addition of porous Co3O4 nanorods enhanced the electrocatalytic activity and ORR kinetics significantly and the overall resistance of the system was greatly reduced. Moreover, the MFC with a higher concentration of the catalyst achieved a maximum power density of 503±16mW/m(2), which was approximately five times higher than the bare graphite electrode. The improved catalytic activity of the cathodes could be due to the porous properties of Co3O4 nanorods that provided the higher number of active sites for oxygen. Copyright © 2016 Elsevier Ltd. All rights reserved.

Molecular approaches to the photocatalytic reduction of carbon dioxide for solar fuels.

PubMed

Morris, Amanda J; Meyer, Gerald J; Fujita, Etsuko

2009-12-21

The scientific community now agrees that the rise in atmospheric CO(2), the most abundant green house gas, comes from anthropogenic sources such as the burning of fossil fuels. This atmospheric rise in CO(2) results in global climate change. Therefore methods for photochemically transforming CO(2) into a source of fuel could offer an attractive way to decrease atmospheric concentrations. One way to accomplish this conversion is through the light-driven reduction of carbon dioxide to methane (CH(4(g))) or methanol (CH(3)OH((l))) with electrons and protons derived from water. Existing infrastructure already supports the delivery of natural gas and liquid fuels, which makes these possible CO(2) reduction products particularly appealing. This Account focuses on molecular approaches to photochemical CO(2) reduction in homogeneous solution. The reduction of CO(2) by one electron to form CO(2)(*-) is highly unfavorable, having a formal reduction potential of -2.14 V vs SCE. Rapid reduction requires an overpotential of up to 0.6 V, due at least in part to the kinetic restrictions imposed by the structural difference between linear CO(2) and bent CO(2)(*-). An alternative and more favorable pathway is to reduce CO(2) though proton-assisted multiple-electron transfer. The development of catalysts, redox mediators, or both that efficiently drive these reactions remains an important and active area of research. We divide these reactions into two class types. In Type I photocatalysis, a molecular light absorber and a transition metal catalyst work in concert. We also consider a special case of Type 1 photocatalysis, where a saturated hydrocarbon links the catalyst and the light absorber in a supramolecular compound. In Type II photocatalysis, the light absorber and the catalyst are the same molecule. In these reactions, transition-metal coordination compounds often serve as catalysts because they can absorb a significant portion of the solar spectrum and can promote activation of small molecules. This Account discusses four classes of transition-metal catalysts: (A) metal tetraaza-macrocyclic compounds; (B) supramolecular complexes; (C) metalloporphyrins and related metallomacrocycles; (D) Re(CO)(3)(bpy)X-based compounds where bpy = 2,2'-bipyridine. Carbon monoxide and formate are the primary CO(2) reduction products, and we also propose bicarbonate/carbonate production. For comprehensiveness, we briefly discuss hydrogen formation, a common side reaction that occurs concurrently with CO(2) reduction, though the details of that process are beyond the scope of this Account. It is our hope that drawing attention both to current mechanistic hypotheses and to the areas that are poorly understood will stimulate research that could one day provide an efficient solution to this global problem.

N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

2017-08-01

It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

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

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O2 + 4e– + 4H+ ⇌ 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc+/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water frommore » aqueous solution to organic solvent, -0.43 kcal mol–1 for MeCN and -1.47 kcal mol–1 for DMF, and the potential of the H+/H2 couple, – 0.028 V in MeCN and -0.662 V in DMF. The H+/H2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple has been extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 and +0.15 V in MeCN and -0.73 and -0.48 V in DMF, respectively. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol–1 for acetonitrile and +0.6 kcal mol–1 for DMF.« less

Microfluidic platform for studying the electrochemical reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Whipple, Devin Talmage

Diminishing supplies of conventional energy sources and growing concern over greenhouse gas emissions present significant challenges to supplying the world's rapidly increasing demand for energy. The electrochemical reduction of carbon dioxide has the potential to address many of these issues by providing a means of storing electricity in chemical form. Storing electrical energy as chemicals is beneficial for leveling the output of clean, but intermittent renewable energy sources such as wind and solar. Electrical energy stored as chemicals can also be used as carbon neutral fuels for portable applications allowing petroleum derived fuels in the transportation sector to be replaced by more environmentally friendly energy sources. However, to be a viable technology, the electrochemical reduction of carbon dioxide needs to have both high current densities and energetic efficiencies (Chapter 1). Although many researchers have studied the electrochemical reduction of CO2 including parameters such as catalysts, electrolytes and temperature, further investigation is needed to improve the understanding of this process and optimize the performance (Chapter 2). This dissertation reports the development and validation of a microfluidic reactor for the electrochemical reduction of CO2 (Chapter 3). The design uses a flowing liquid electrolyte instead of the typical polymer electrolyte membrane. In addition to other benefits, this flowing electrolyte gives the reactor great flexibility, allowing independent analysis of each electrode and the testing of a wide variety of conditions. In this work, the microfluidic reactor has been used in the following areas: • Comparison of different metal catalysts for the reduction of CO2 to formic acid and carbon monoxide (Chapter 4). • Investigation of the effects of the electrolyte pH on the reduction of CO2 to formic acid and carbon monoxide (Chapter 5). • Study of amine based electrolytes for lowering the overpotentials for CO2 reduction and suppressing undesirable hydrogen evolution (Chapter 6). • Investigation of the effects of reaction temperature on the Faradaic efficiency and current density for CO2 reduction on several catalysts (Chapter 7). These studies demonstrate the utility of this flexible reactor design and provide increased understanding of the electrochemical reduction of CO2 and the critical parameters for optimization of this process.

Coupling molecular catalysts with nanostructured surfaces for efficient solar fuel production

NASA Astrophysics Data System (ADS)

Jin, Tong

Solar fuel generation via carbon dioxide (CO2) reduction is a promising approach to meet the increasing global demand for energy and to minimize the impact of energy consumption on climate change. However, CO2 is thermodynamically stable; its activation often requires the use of appropriate catalysts. In particular, molecular catalysts with well-defined structures and tunability have shown excellent activity in photochemical CO2 reduction. These homogenous catalysts, however, suffer from poor stability under photochemical conditions and difficulty in recycling from the reaction media. Heterogenized molecular catalysts, particularly those prepared by coupling molecular catalysts with solid-state surfaces, have attracted more attention in recent years as potential solutions to address the issues associated with molecular catalysts. In this work, solar CO2 reduction is investigated using systems coupling molecular catalysts with robust nanostructured surfaces. In Chapter 2, heterogenization of macrocyclic cobalt(III) and nickel (II) complexes on mesoporous silica surface was achieved by different methods. Direct ligand derivatization significantly lowered the catalytic activity of Co(III) complex, while grafting the Co(III) complex onto silica surface through Si-O-Co linkage resulted in hybrid catalysts with excellent activity in CO2 reduction in the presence of p-terphenyl as a molecular photosensitizer. An interesting loading effect was observed, in which the optimal activity was achieved at a medium Co(III) surface density. Heterogenization of the Ni(II) complex on silica surface has also been implemented, the poor photocatalytic activity of the hybrid catalyst can be attributed to the intrinsic nature of the homogeneous analogue. This study highlighted the importance of appropriate linking strategies in preparing functional heterogenized molecular catalysts. Coupling molecular complexes with light-harvesting surfaces could avoid the use of expensive molecular photosensitizers. In Chapter 3, effective coupling of the macrocyclic Co(III) complex with titanium dioxide (TiO¬2) nanoparticles was achieved by two deposition methods. The synthesized hybrid photocatalysts were thoroughly characterized with a variety of techniques. Upon UV light irradiation, photoexcited electrons in TiO2 nanoparticles were transferred to the surface Co(III) catalyst for CO2 reduction. Production of carbon monoxide (CO) from CO2 was confirmed by isotope labeling combined with infrared spectroscopy. Deposition of the Co(III) catalyst through Ti-O-Co linkages was essential for the photo-induced electron transfer and CO2-reduction activity using the hybrid photocatalysts. In Chapter 4, molecular Re(I) and Co(II) catalysts were coupled with silicon-based photoelectrodes, including a silicon nanowire (SiNW) photoelectrode, to achieve photoelectrochemical CO2 reduction. Photovoltages between 300-600 mV were obtained using the molecular catalysts on the silicon photoelectrodes. SiNWs exhibited enhanced properties, including significantly higher photovoltages than a planar silicon photoelectrode, the ability to protect one of the molecular catalysts from photo-induced decomposition, and excellent selectivity towards CO production in CO2 reduction. Recent theoretical and experimental work have demonstrated low-energy, binuclear pathways for CO2-to-CO conversion using several molecular catalysts. In such binuclear pathways, two metal centers work cooperatively to achieve two-electron CO2 reduction. Chapter 5 describes our effort to promote the binuclear pathway by grafting the molecular Co(III) catalyst onto silica surfaces. Different linking strategies were attempted to achieve this goal by planting the surface Co(III) sites in close proximity.

NiCo2O4/N-doped graphene as an advanced electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Zhang, Hui; Li, Huiyong; Wang, Haiyan; He, Kejian; Wang, Shuangyin; Tang, Yougen; Chen, Jiajie

2015-04-01

Developing low-cost catalyst for high-performance oxygen reduction reaction (ORR) is highly desirable. Herein, NiCo2O4/N-doped reduced graphene oxide (NiCo2O4/N-rGO) hybrid is proposed as a high-performance catalyst for ORR for the first time. The well-formed NiCo2O4/N-rGO hybrid is studied by cyclic voltammetry (CV) curves and linear-sweep voltammetry (LSV) performed on the rotating-ring-disk-electrode (RDE) in comparison with N-rGO-free NiCo2O4 and the bare N-rGO. Due to the synergistic effect, the NiCo2O4/N-rGO hybrid exhibits significant improvement of catalytic performance with an onset potential of -0.12 V, which mainly favors a direct four electron pathway in ORR process, close to the behavior of commercial carbon-supported Pt. Also, the benefits of N-incorporation are investigated by comparing NiCo2O4/N-rGO with NiCo2O4/rGO, where higher cathodic currents, much more positive half-wave potential and more electron transfer numbers are observed for the N-doping one, which should be ascribed to the new highly efficient active sites created by N incorporation into graphene. The NiCo2O4/N-rGO hybrid could be used as a promising catalyst for high power metal/air battery.

CO2 mitigation potential of mineral carbonation with industrial alkalinity sources in the United States.

PubMed

Kirchofer, Abby; Becker, Austin; Brandt, Adam; Wilcox, Jennifer

2013-07-02

The availability of industrial alkalinity sources is investigated to determine their potential for the simultaneous capture and sequestration of CO2 from point-source emissions in the United States. Industrial alkalinity sources investigated include fly ash, cement kiln dust, and iron and steel slag. Their feasibility for mineral carbonation is determined by their relative abundance for CO2 reactivity and their proximity to point-source CO2 emissions. In addition, the available aggregate markets are investigated as possible sinks for mineral carbonation products. We show that in the U.S., industrial alkaline byproducts have the potential to mitigate approximately 7.6 Mt CO2/yr, of which 7.0 Mt CO2/yr are CO2 captured through mineral carbonation and 0.6 Mt CO2/yr are CO2 emissions avoided through reuse as synthetic aggregate (replacing sand and gravel). The emission reductions represent a small share (i.e., 0.1%) of total U.S. CO2 emissions; however, industrial byproducts may represent comparatively low-cost methods for the advancement of mineral carbonation technologies, which may be extended to more abundant yet expensive natural alkalinity sources.

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.

Thermogravimetric, Calorimetric, and Structural Studies of the Co3 O4 /CoO Oxidation/Reduction Reaction

NASA Astrophysics Data System (ADS)

Unruh, Karl; Cichocki, Ronald; Kelly, Brian; Poirier, Gerald

2015-03-01

To better assess the potential of cobalt oxide for thermal energy storage (TES), the Co3O4/CoO oxidation/reduction reaction has been studied by thermogravimetric (TGA), calorimetric (DSC), and x-ray diffraction (XRD) measurements in N2 and atmospheric air environments. TGA measurements showed an abrupt mass loss of about 6.6% in both N2 and air, consistent with the stoichiometric reduction of Co3O4 to CoO and structural measurements. The onset temperature of the reduction of Co3O4 in air was only weakly dependent on the sample heating rate and occurred at about 910 °C. The onset temperature for the oxidation of CoO varied between about 850 and 875 °C for cooling rates between 1 and 20 °C/min, but complete re-conversion to Co3O4 could only be achieved at the slowest cooling rates. Due to the dependence of the rate constant on the oxygen partial pressure, the oxidation of Co3O4 in a N2 environment occurred at temperatures between about 775 and 825 °C for heating rates between 1 and 20 °C/min and no subsequent re-oxidation of the reduced Co3O4 was observed on cooling to room temperature. In conjunction with a measured transition heat of about 600 J/g of Co3O4, these measurements indicate that cobalt oxide is a viable TES material.

H2 enrichment from synthesis gas by Desulfotomaculum carboxydivorans for potential applications in synthesis gas purification and biodesulfurization.

PubMed

Sipma, Jan; Osuna, M Begoña; Parshina, Sofiya N; Lettinga, Gatze; Stams, Alfons J M; Lens, Piet N L

2007-08-01

Desulfotomaculum carboxydivorans, recently isolated from a full-scale anaerobic wastewater treatment facility, is a sulfate reducer capable of hydrogenogenic growth on carbon monoxide (CO). In the presence of sulfate, the hydrogen formed is used for sulfate reduction. The organism grows rapidly at 200 kPa CO, pH 7.0, and 55 degrees C, with a generation time of 100 min, producing nearly equimolar amounts of H(2) and CO(2) from CO and H(2)O. The high specific CO conversion rates, exceeding 0.8 mol CO (g protein)(-1) h(-1), makes this bacterium an interesting candidate for a biological alternative of the currently employed chemical catalytic water-gas shift reaction to purify synthesis gas (contains mainly H(2), CO, and CO(2)). Furthermore, as D. carboxydivorans is capable of hydrogenotrophic sulfate reduction at partial CO pressures exceeding 100 kPa, it is also a good candidate for biodesulfurization processes using synthesis gas as electron donor at elevated temperatures, e.g., in biological flue gas desulfurization. Although high maximal specific sulfate reduction rates (32 mmol (g protein)(-1) h(-1)) can be obtained, its sulfide tolerance is rather low and pH dependent, i.e., maximally 9 and 5 mM sulfide at pH 7.2 and pH 6.5, respectively.

Evaluating molecular cobalt complexes for the conversion of N2 to NH3.

PubMed

Del Castillo, Trevor J; Thompson, Niklas B; Suess, Daniel L M; Ung, Gaël; Peters, Jonas C

2015-10-05

Well-defined molecular catalysts for the reduction of N2 to NH3 with protons and electrons remain very rare despite decades of interest and are currently limited to systems featuring molybdenum or iron. This report details the synthesis of a molecular cobalt complex that generates superstoichiometric yields of NH3 (>200% NH3 per Co-N2 precursor) via the direct reduction of N2 with protons and electrons. While the NH3 yields reported herein are modest by comparison to those of previously described iron and molybdenum systems, they intimate that other metals are likely to be viable as molecular N2 reduction catalysts. Additionally, a comparison of the featured tris(phosphine)borane Co-N2 complex with structurally related Co-N2 and Fe-N2 species shows how remarkably sensitive the N2 reduction performance of potential precatalysts is. These studies enable consideration of the structural and electronic effects that are likely relevant to N2 conversion activity, including the π basicity, charge state, and geometric flexibility.

Synthesis and characterization of (Ni{sub 1−x}Co{sub x})Se{sub 2} based ternary selenides as electrocatalyst for triiodide reduction in dye-sensitized solar cells

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

Theerthagiri, J.; Senthil, R.A.; Buraidah, M.H.

2016-06-15

Ternary metal selenides of (Ni{sub 1−x}Co{sub x})Se{sub 2} with 0≤x≤1 were synthesized by using one-step hydrothermal reduction route. The synthesized metal selenides were utilized as an efficient, low-cost platinum free counter electrode for dye-sensitized solar cells. The cyclic voltammetry and electrochemical impedance spectroscopy studies revealed that the Ni{sub 0.5}Co{sub 0.5}Se{sub 2} counter electrode exhibited higher electrocatalytic activity and lower charge transfer resistance at the counter electrode/electrolyte interface than the other compositions for reduction of triiodide to iodide. Ternary selenides of Ni{sub 0.5}Co{sub 0.5}Se{sub 2} offer a synergistic effect to the electrocatalytic activity for the reduction of triiodide that might bemore » due to an increase in active catalytic sites and small charge transfer resistance. The DSSC with Ni{sub 0.5}Co{sub 0.5}Se{sub 2} counter electrode achieved a high power conversion efficiency of 6.02%, which is comparable with that of conventional platinum counter electrode (6.11%). This present investigation demonstrates the potential application of Ni{sub 0.5}Co{sub 0.5}Se{sub 2} as counter electrode in dye-sensitized solar cells.« less

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

DOE PAGES

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.; ...

2018-02-09

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

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

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Stability of carbon electrodes for aqueous lithium-air secondary batteries

NASA Astrophysics Data System (ADS)

Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2014-01-01

The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

Cofactor and CO2 donor regulation involved in reductive routes for polymalic acid production by Aureobasidium pullulans CCTCC M2012223.

PubMed

Zou, Xiang; Tu, Guangwei; Zan, Zhanquan

2014-10-01

Polymalic acid (PMA) is a water-soluble polyester with many attractive properties for biomedical application. Its monomer L-malic acid is widely used in the food industry and also a potential C4 platform chemical. Cofactor and CO2 donor involved in the reductive routes were investigated for PMA production by Aureobasidium pullulans. Biotin as the key cofactor of pyruvate carboxylase was favor for the PMA biosynthesis. Na2CO3 as CO2 donor can obviously improved PMA titer when compared with no CO2 supplier NaOH, and also exhibit more advantages than the other donor CaCO3 because of its water-soluble characteristic. A combinational process with addition of biotin 70 mg/L and Na2CO3 as the CO2 donor was scaled-up in 50 L fermentor, achieving the high product 34.3 g/L of PMA and productivity of 0.41 g/L h. This process provides an efficient and economical way for PMA and malic acid production, and is promising for industrial application.

Heterogeneous catalytic conversion of CO2: a comprehensive theoretical review.

PubMed

Li, Yawei; Chan, Siew Hwa; Sun, Qiang

2015-05-21

The conversion of CO2 into fuels and useful chemicals has been intensively pursued for renewable, sustainable and green energy. However, due to the negative adiabatic electron affinity (EA) and large ionization potential (IP), the CO2 molecule is chemically inert, thus making the conversion difficult under normal conditions. Novel catalysts, which have high stability, superior efficiency and low cost, are urgently needed to facilitate the conversion. As the first step to design such catalysts, understanding the mechanisms involved in CO2 conversion is absolutely indispensable. In this review, we have summarized the recent theoretical progress in mechanistic studies based on density functional theory, kinetic Monte Carlo simulation, and microkinetics modeling. We focus on reaction channels, intermediate products, the key factors determining the conversion of CO2 in solid-gas interface thermocatalytic reduction and solid-liquid interface electrocatalytic reduction. Furthermore, we have proposed some possible strategies for improving CO2 electrocatalysis and also discussed the challenges in theory, model construction, and future research directions.

A Nitrogen-Doped Carbon Catalyst for Electrochemical CO2 Conversion to CO with High Selectivity and Current Density.

PubMed

Jhong, Huei-Ru Molly; Tornow, Claire E; Smid, Bretislav; Gewirth, Andrew A; Lyth, Stephen M; Kenis, Paul J A

2017-03-22

We report characterization of a non-precious metal-free catalyst for the electrochemical reduction of CO 2 to CO; namely, a pyrolyzed carbon nitride and multiwall carbon nanotube composite. This catalyst exhibits a high selectivity for production of CO over H 2 (approximately 98 % CO and 2 % H 2 ), as well as high activity in an electrochemical flow cell. The CO partial current density at intermediate cathode potentials (V=-1.46 V vs. Ag/AgCl) is up to 3.5× higher than state-of-the-art Ag nanoparticle-based catalysts, and the maximum current density is 90 mA cm -2 . The mass activity and energy efficiency (up to 48 %) were also higher than the Ag nanoparticle reference. Moving away from precious metal catalysts without sacrificing activity or selectivity may significantly enhance the prospects of electrochemical CO 2 reduction as an approach to reduce atmospheric CO 2 emissions or as a method for load-leveling in relation to the use of intermittent renewable energy sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of CO2 emission reduction strategy from in-use gasoline vehicle

NASA Astrophysics Data System (ADS)

Choudhary, Arti; Gokhale, Sharad

2016-04-01

On road transport emissions is kicking off in Indian cities due to high levels of urbanization and economic growth during the last decade in Indian subcontinent. In 1951, about 17% of India's population were living in urban areas that increased to 32% in 2011. Currently, India is fourth largest Green House Gas (GHG) emitter in the world, with its transport sector being the second largest contributor of CO2 emissions. For achieving prospective carbon reduction targets, substantial opportunity among in-use vehicle is necessary to quantify. Since, urban traffic flow and operating condition has significant impact on exhaust emission (Choudhary and Gokhale, 2016). This study examined the influence of vehicular operating kinetics on CO2 emission from predominant private transportation vehicles of Indian metropolitan city, Guwahati. On-board instantaneous data were used to quantify the impact of CO2 emission on different mileage passenger cars and auto-rickshaws at different times of the day. Further study investigates CO2 emission reduction strategies by using International Vehicle Emission (IVE) model to improve co-benefit in private transportation by integrated effort such as gradual phase-out of inefficient vehicle and low carbon fuel. The analysis suggests that fuel type, vehicles maintenance and traffic flow management have potential for reduction of urban sector GHG emissions. Keywords: private transportation, CO2, instantaneous emission, IVE model Reference Choudhary, A., Gokhale, S. (2016). Urban real-world driving traffic emissions during interruption and congestion. Transportation Research Part D: Transport and Environment 43: 59-70.

Zirconium and silver co-doped TiO2 nanoparticles as visible light catalyst for reduction of 4-nitrophenol, degradation of methyl orange and methylene blue

NASA Astrophysics Data System (ADS)

Naraginti, Saraschandra; Stephen, Finian Bernard; Radhakrishnan, Adhithya; Sivakumar, A.

2015-01-01

Catalytic activity of Zr and Ag co-doped TiO2 nanoparticles on the reduction of 4-nitrophenol, degradation of methylene blue and methyl orange was studied using sodium borohydride as reducing agent. The nanoparticles were characterized using X-ray diffraction, energy dispersive X-ray, high resolution transmission electron microscopy, selected area electron diffraction and UV-Vis spectroscopy. The rate of the reduction/degradation was found to increase with increasing amount of the photocatalyst which could be attributed to higher dispersity and small size of the nanoparticles. The catalytic activity of Zr and Ag co-doped TiO2 nanoparticles showed no significant difference even after recycling the catalyst four times indicating a promising potential for industrial application of the prepared photocatalyst.

Secondary coordination sphere interactions within the biomimetic iron azadithiolate complexes related to Fe-only hydrogenase: dynamic measure of electron density about the Fe sites.

PubMed

Liu, Yu-Chiao; Tu, Ling-Kuang; Yen, Tao-Hung; Lee, Gene-Hsiang; Yang, Shu-Ting; Chiang, Ming-Hsi

2010-07-19

A series of iron azadithiolate complexes possessing an intramolecular secondary coordination sphere interaction and an ability to reduce HOAc at the potential near the first electron-transfer process are reported. A unique structural feature in which the aza nitrogen has its lone pair point toward the apical carbonyl carbon is observed in [Fe(2)(mu-S(CH(2))(2)NR(CH(2))(2)S)(CO)(6-x)L(x)](2) (R = (n)Pr, x = 0, 1a; R = (i)Pr, x = 0, 1b; R = (n)Pr, L = PPh(3), x = 1, 2; R = (n)Pr, L = P(n)Bu(3), x = 1, 3) as biomimetic models of the active site of Fe-only hydrogenase. The presence of this weak N...C(CO(ap)) interaction provides electronic perturbation at the Fe center. The distance of the N...C(CO(ap)) contact is 3.497 A in 1a. It increases by 0.455 A in 2 when electronic density of the Fe site is slightly enriched by a weak sigma-donating ligand, PPh(3). A longer distance (4.040 A) is observed for the P(n)Bu(3) derivative, 3. This N...C(CO(ap)) distance is thus a dynamic measure of electronic nature of the Fe(2) core. Variation of electronic richness within the Fe(2) moiety among the complexes reflects on their electrochemical response. Reduction of 2 is recorded at the potential of -2.17 V, which is 270 mV more negative than that of 1. Complex 3 requires additional 150 mV for the same reduction. Such cathodic shift results from CO substitution by phosphines. Electrocatalytic hydrogen production from HOAc by both kinds of complexes (all-CO and phosphine-substituted species) requires the potential close to that for reduction of the parent molecules in the absence of acids. The catalytic mechanism of 1a is proposed to involve proton uptake at the Fe(0)Fe(I) redox level instead of the Fe(0)Fe(0) level. This result is the first observation among the all-CO complexes with respect to electrocatalysis of HOAc.

Investigations by Protein Film Electrochemistry of Alternative Reactions of Nickel-Containing Carbon Monoxide Dehydrogenase.

PubMed

Wang, Vincent C-C; Islam, Shams T A; Can, Mehmet; Ragsdale, Stephen W; Armstrong, Fraser A

2015-10-29

Protein film electrochemistry has been used to investigate reactions of highly active nickel-containing carbon monoxide dehydrogenases (CODHs). When attached to a pyrolytic graphite electrode, these enzymes behave as reversible electrocatalysts, displaying CO2 reduction or CO oxidation at minimal overpotential. The O2 sensitivity of CODH is suppressed by adding cyanide, a reversible inhibitor of CO oxidation, or by raising the electrode potential. Reduction of N2O, isoelectronic with CO2, is catalyzed by CODH, but the reaction is sluggish, despite a large overpotential, and results in inactivation. Production of H2 and formate under highly reducing conditions is consistent with calculations predicting that a nickel-hydrido species might be formed, but the very low rates suggest that such a species is not on the main catalytic pathway.

Soil CO2 concentrations and efflux dynamics of a tree island in the Pantanal wetland

NASA Astrophysics Data System (ADS)

Lathuillière, Michael J.; Pinto, Osvaldo B.; Johnson, Mark S.; Jassal, Rachhpal S.; Dalmagro, Higo J.; Leite, Nei K.; Speratti, Alicia B.; Krampe, Daniela; Couto, Eduardo G.

2017-08-01

The Pantanal is the largest tropical wetland on the planet, and yet little information is available on the biome's carbon cycle. We used an automatic station to measure soil CO2 concentrations and oxidation-reduction potential over the 2014 and 2015 flood cycles of a tree island in the Pantanal that is immune to inundation during the wetland's annual flooding. The soil CO2 concentration profile was then used to estimate soil CO2 efflux over the two periods. In 2014, subsurface soil saturation at 0.30 m depth created conditions in that layer that led to CO2 buildup close to 200,000 ppm and soil oxidation-reduction potential below -300 mV, conditions that were not repeated in 2015 due to annual variability in soil saturation at the site. Mean CO2 efflux over the 2015 flood cycle was 0.023 ± 0.103 mg CO2-C m-2 s-1 representing a total annual efflux of 593 ± 2690 mg CO2-C m-2 y-1. Unlike a nearby tree island site that experiences full inundation during the wet season, here the soil dried quickly following repeated rain events throughout the year, which led to the release of CO2 pulses from the soil. This study highlights not only the complexity and heterogeneity in the Pantanal's carbon balance based on differences in topography, flood cycles, and vegetation but also the challenges of applying the gradient method in the Pantanal due to deviations from steady state conditions.

CO2 Capture and Conversion on Rutile TiO2(110) in the Water Environment: Insight by First-Principles Calculations.

PubMed

Yin, Wen-Jin; Krack, Matthias; Wen, Bo; Ma, Shang-Yi; Liu, Li-Min

2015-07-02

The conversion of CO2 by the virtue of sunlight has the great potential to produce useful fuels or valuable chemicals while decreasing CO2 emission from the traditional fossil fuels. Here, we use the first-principles calculations combined with the periodic continuum solvation model (PCSM) to explore the adsorption and reactivity of CO2 on rutile TiO2(110) in the water environment. The results exhibit that both adsorption structures and reactivity of CO2 are greatly affected by water coadsorption on rutile TiO2(110). In particular, the solvation effect can change the most stable adsorption configuration of CO2 and H2O on rutile TiO2(110). In addition, the detailed conversion mechanism of CO2 reduction is further explored in the water environment. The results reveal that the solvation effect cannot only greatly decrease the energy barrier of CO2 reduction but also affect the selectivity of the reaction processes. These results presented here show the importance of the aqueous solution, which should be helpful to understand the detailed reaction processes of photocatalysts.

Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

PubMed Central

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-01-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

Passive Biobarrier for Treating Co-mingled Perchlorate and RDX in Groundwater at an Active Range

DTIC Science & Technology

2016-05-12

and Groundwater Temperature ............................. 102 6.1.2 Dissolved Oxygen (DO) and Oxidation Reduction Potential (ORP...22 or equivalent). Parameters, including temperature , conductivity, dissolved oxygen , oxidation-reduction potential (ORP), turbidity, and pH were...3% for temperature and specific conductivity, and ᝺% for dissolved oxygen , ORP, and turbidity. When parameters were stable according to the above

Global cost estimates of reducing carbon emissions through avoided deforestation

PubMed Central

Kindermann, Georg; Obersteiner, Michael; Sohngen, Brent; Sathaye, Jayant; Andrasko, Kenneth; Rametsteiner, Ewald; Schlamadinger, Bernhard; Wunder, Sven; Beach, Robert

2008-01-01

Tropical deforestation is estimated to cause about one-quarter of anthropogenic carbon emissions, loss of biodiversity, and other environmental services. United Nations Framework Convention for Climate Change talks are now considering mechanisms for avoiding deforestation (AD), but the economic potential of AD has yet to be addressed. We use three economic models of global land use and management to analyze the potential contribution of AD activities to reduced greenhouse gas emissions. AD activities are found to be a competitive, low-cost abatement option. A program providing a 10% reduction in deforestation from 2005 to 2030 could provide 0.3–0.6 Gt (1 Gt = 1 × 105 g) CO2·yr−1 in emission reductions and would require $0.4 billion to $1.7 billion·yr−1 for 30 years. A 50% reduction in deforestation from 2005 to 2030 could provide 1.5–2.7 Gt CO2·yr−1 in emission reductions and would require $17.2 billion to $28.0 billion·yr−1. Finally, some caveats to the analysis that could increase costs of AD programs are described. PMID:18650377

Selective CO2 reduction conjugated with H2O oxidation utilizing semiconductor/metal-complex hybrid photocatalysts

NASA Astrophysics Data System (ADS)

Morikawa, T.; Sato, S.; Arai, T.; Uemura, K.; Yamanaka, K. I.; Suzuki, T. M.; Kajino, T.; Motohiro, T.

2013-12-01

We developed a new hybrid photocatalyst for CO2 reduction, which is composed of a semiconductor and a metal complex. In the hybrid photocatalyst, ΔG between the position of conduction band minimum (ECBM) of the semiconductor and the CO2 reduction potential of the complex is an essential factor for realizing fast electron transfer from the conduction band of semiconductor to metal complex leading to high photocatalytic activity. On the basis of this concept, the hybrid photocatalyst InP/Ru-complex, which functions in aqueous media, was developed. The photoreduction of CO2 to formate using water as an electron donor and a proton source was successfully achieved as a Z-scheme system by functionally conjugating the InP/Ru-complex photocatalyst for CO2 reduction with a TiO2 photocatalyst for water oxidation. The conversion efficiency from solar energy to chemical energy was ca. 0.04%, which approaches that for photosynthesis in a plant. Because this system can be applied to many other inorganic semiconductors and metal-complex catalysts, the efficiency and reaction selectivity can be enhanced by optimization of the electron transfer process including the energy-band configurations, conjugation conformations, and catalyst structures. This electrical-bias-free reaction is a huge leap forward for future practical applications of artificial photosynthesis under solar irradiation to produce organic species.

Simulating the potential for Carbon Dioxide (CO2) reduction by the application of environmentally friendly transportation (case study: Gatot Subroto Street, Medan City)

NASA Astrophysics Data System (ADS)

Suryati, Isra; Turmuzi Lubis, Muhammad; Mawaddah, Nurul

2018-03-01

Carbon Dioxide (CO2) is one of the greenhouse gases. One source of greenhouse gases comes from the use of fossil fuels from the transport sector. The transportation sector is one of the dominant sectors in contributing to the greenhouse effect. This study aims to calculate the amount of CO2 from transportation activities by using mobile six equations in Gatot Subroto Street, Medan City. A sampling of CO2 concentration was done using Carbon Dioxide Monitor with Non-Dispersive Infra Red (NDIR) Analyzer method. Also, a simulation of the reduction of the number of private vehicles to mass transportation such as BRT gas-fired. The results showed CO2 emissions calculations with mobile six ranged from 47.2 kg CO2 - 978.2 kg CO2. Meanwhile, measurements range from 3,004 ppm - 3,405 ppm. Implementation of the concept of environmentally friendly transportation such as BRT in Gatot Subroto Street, Medan City will be able to reduce the average emissions load CO2 by 42.75% -78.80%. Based on the calculation simulation in this study is estimated the number of BRT required approximately 71 units.

Burrows of the semi-terrestrial crab Ucides cordatus enhance CO2 release in a North Brazilian mangrove forest.

PubMed

Pülmanns, Nathalie; Diele, Karen; Mehlig, Ulf; Nordhaus, Inga

2014-01-01

Ucides cordatus is an abundant mangrove crab in Brazil constructing burrows of up to 2 m depth. Sediment around burrows may oxidize during low tides. This increase in sediment-air contact area may enhance carbon degradation processes. We hypothesized that 1) the sediment CO2 efflux rate is greater with burrows than without and 2) the reduction potential in radial profiles in the sediment surrounding the burrows decreases gradually, until approximating non-bioturbated conditions. Sampling was conducted during the North Brazilian wet season at neap tides. CO2 efflux rates of inhabited burrows and plain sediment were measured with a CO2/H2O gas analyzer connected to a respiration chamber. Sediment redox potential, pH and temperature were measured in the sediment surrounding the burrows at horizontal distances of 2, 5, 8 and 15 cm at four sediment depths (1, 10, 30 and 50 cm) and rH values were calculated. Sediment cores (50 cm length) were taken to measure the same parameters for plain sediment. CO2 efflux rates of plain sediment and individual crab burrows with entrance diameters of 7 cm were 0.7-1.3 µmol m(-2) s(-1) and 0.2-0.4 µmol burrows(-1) s(-1), respectively. CO2 released from a Rhizophora mangle dominated forest with an average of 1.7 U. cordatus burrows(-1) m(-2) yielded 1.0-1.7 µmol m(-2) s(-1), depending on the month and burrow entrance diameter. Laboratory experiments revealed that 20-60% of the CO2 released by burrows originated from crab respiration. Temporal changes in the reduction potential in the sediment surrounding the burrows did not influence the CO2 release from burrows. More oxidized conditions of plain sediment over time may explain the increase in CO2 release until the end of the wet season. CO2 released by U. cordatus and their burrows may be a significant pathway of CO2 export from mangrove sediments and should be considered in mangrove carbon budget estimates.

Burrows of the Semi-Terrestrial Crab Ucides cordatus Enhance CO2 Release in a North Brazilian Mangrove Forest

PubMed Central

Pülmanns, Nathalie; Diele, Karen; Mehlig, Ulf; Nordhaus, Inga

2014-01-01

Ucides cordatus is an abundant mangrove crab in Brazil constructing burrows of up to 2 m depth. Sediment around burrows may oxidize during low tides. This increase in sediment-air contact area may enhance carbon degradation processes. We hypothesized that 1) the sediment CO2 efflux rate is greater with burrows than without and 2) the reduction potential in radial profiles in the sediment surrounding the burrows decreases gradually, until approximating non-bioturbated conditions. Sampling was conducted during the North Brazilian wet season at neap tides. CO2 efflux rates of inhabited burrows and plain sediment were measured with a CO2/H2O gas analyzer connected to a respiration chamber. Sediment redox potential, pH and temperature were measured in the sediment surrounding the burrows at horizontal distances of 2, 5, 8 and 15 cm at four sediment depths (1, 10, 30 and 50 cm) and rH values were calculated. Sediment cores (50 cm length) were taken to measure the same parameters for plain sediment. CO2 efflux rates of plain sediment and individual crab burrows with entrance diameters of 7 cm were 0.7–1.3 µmol m−2 s−1 and 0.2–0.4 µmol burrows−1 s−1, respectively. CO2 released from a Rhizophora mangle dominated forest with an average of 1.7 U. cordatus burrows−1 m−2 yielded 1.0–1.7 µmol m−2 s−1, depending on the month and burrow entrance diameter. Laboratory experiments revealed that 20–60% of the CO2 released by burrows originated from crab respiration. Temporal changes in the reduction potential in the sediment surrounding the burrows did not influence the CO2 release from burrows. More oxidized conditions of plain sediment over time may explain the increase in CO2 release until the end of the wet season. CO2 released by U. cordatus and their burrows may be a significant pathway of CO2 export from mangrove sediments and should be considered in mangrove carbon budget estimates. PMID:25313661

Enhanced photocatalytic CO₂-reduction activity of electrospun mesoporous TiO₂ nanofibers by solvothermal treatment.

PubMed

Fu, Junwei; Cao, Shaowen; Yu, Jiaguo; Low, Jingxiang; Lei, Yongpeng

2014-06-28

Photocatalytic reduction of CO2 into renewable hydrocarbon fuels using semiconductor photocatalysts is considered as a potential solution to the energy deficiency and greenhouse effect. In this work, mesoporous TiO2 nanofibers with high specific surface areas and abundant surface hydroxyl groups are prepared using an electrospinning strategy combined with a subsequent calcination process, followed by a solvothermal treatment. The solvothermally treated mesoporous TiO2 nanofibers exhibit excellent photocatalytic performance on CO2 reduction into hydrocarbon fuels. The significantly improved photocatalytic activity can be attributed to the enhanced CO2 adsorption capacity and the improved charge separation after solvothermal treatment. The highest activity is achieved for the sample with a 2-h solvothermal treatment, showing 6- and 25-fold higher CH4 production rate than those of TiO2 nanofibers without solvothermal treatment and P25, respectively. This work may also provide a prototype for studying the effect of solvothermal treatment on the structure and photocatalytic activity of semiconductor photocatalysts.

Quantifying the air quality-CO2 tradeoff potential for airports

NASA Astrophysics Data System (ADS)

Ashok, Akshay; Dedoussi, Irene C.; Yim, Steve H. L.; Balakrishnan, Hamsa; Barrett, Steven R. H.

2014-12-01

Aircraft movements on the airport surface are responsible for CO2 emissions that contribute to climate change and other emissions that affect air quality and human health. While the potential for optimizing aircraft surface movements to minimize CO2 emissions has been assessed, the implications of CO2 emissions minimization for air quality have not been quantified. In this paper, we identify conditions in which there is a tradeoff between CO2 emissions and population exposure to O3 and secondary PM2.5 - i.e. where decreasing fuel burn (which is directly proportional to CO2 emissions) results in increased exposure. Fuel burn and emissions are estimated as a function of thrust setting for five common gas turbine engines at 34 US airports. Regional air quality impacts, which are dominated by ozone and secondary PM2.5, are computed as a function of airport location and time using the adjoint of the GEOS-Chem chemistry-transport model. Tradeoffs between CO2 emissions and population exposure to PM2.5 and O3 occur between 2-18% and 5-60% of the year, respectively, depending on airport location, engine type, and thrust setting. The total duration of tradeoff conditions is 5-12 times longer at maximum thrust operations (typical for takeoff) relative to 4% thrust operations (typical for taxiing). Per kilogram of additional fuel burn at constant thrust setting during tradeoff conditions, reductions in population exposure to PM2.5 and O3 are 6-13% and 32-1060% of the annual average (positive) population exposure per kilogram fuel burn, where the ranges encompass the medians over the 34 airports. For fuel burn increases due to thrust increases (i.e. for constant operating time), reductions in both PM2.5 and O3 exposure are 1.5-6.4 times larger in magnitude than those due to increasing fuel burn at constant thrust (i.e. increasing operating time). Airports with relatively high population exposure reduction potentials - which occur due to a combination of high duration and magnitude of tradeoff conditions - are identified. Our results are the first to quantify the extent of the tradeoff between CO2 emissions and air quality impacts at airports. This raises the possibility of reducing the air quality impacts of airports beyond minimizing fuel burn and/or optimizing for minimum net environmental impact.

Reduction of CO2 emission by INCAM model in Malaysia biomass power plants during the year 2016.

PubMed

Amin, Nor Aishah Saidina; Talebian-Kiakalaieh, Amin

2018-03-01

As the world's second largest palm oil producer and exporter, Malaysia could capitalize on its oil palm biomass waste for power generation. The emission factors from this renewable energy source are far lower than that of fossil fuels. This study applies an integrated carbon accounting and mitigation (INCAM) model to calculate the amount of CO 2 emissions from two biomass thermal power plants. The CO 2 emissions released from biomass plants utilizing empty fruit bunch (EFB) and palm oil mill effluent (POME), as alternative fuels for powering steam and gas turbines, were determined using the INCAM model. Each section emitting CO 2 in the power plant, known as the carbon accounting center (CAC), was measured for its carbon profile (CP) and carbon index (CI). The carbon performance indicator (CPI) included electricity, fuel and water consumption, solid waste and waste-water generation. The carbon emission index (CEI) and carbon emission profile (CEP), based on the total monthly carbon production, were determined across the CPI. Various innovative strategies resulted in a 20%-90% reduction of CO 2 emissions. The implementation of reduction strategies significantly reduced the CO 2 emission levels. Based on the model, utilization of EFB and POME in the facilities could significantly reduce the CO 2 emissions and increase the potential for waste to energy initiatives. Copyright © 2017 Elsevier Ltd. All rights reserved.

Necessary and sufficient conditions for the successful three-phase photocatalytic reduction of CO2 by H2O over heterogeneous photocatalysts.

PubMed

Teramura, Kentaro; Tanaka, Tsunehiro

2018-03-28

Artificial photosynthesis has recently drawn an increasing amount of attention due to the fact that it allows for direct solar-to-chemical energy conversion. However, one of the basic steps of this process, namely the reduction of CO2 by H2O to afford O2 and CO2 reduction products (CO2RPs) such as HCOOH, CO, HCHO, CH3OH, and CH4, is very difficult to achieve. In contrast to the CO2 reduction in plants and homogenous systems, the reduction of CO2 to CO2RPs over heterogeneous photocatalysts was challenged by the competing reduction of H+ to H2. Unfortunately, most of the research performed so far has focused only on the reduction of CO2, rather than the characterization of the H2O oxidation and H2 production. Moreover, the fact that the heterogeneous photocatalytic reduction of CO2 into CO2RPs by H2O should satisfy several selectivity criteria has often been ignored. Herein, we propose three such evaluation criteria, namely (1) the origin of carbon in CO2RPs (determined using isotopically labeled CO2 (13CO2)), (2) the relative amount of H2 and CO2RPs produced, and (3) the amount of O2 produced by the oxidation of H2O. If all these criteria are satisfied, i.e., the carbons of CO2RPs originate from CO2, the amount of H2 produced is negligible, and a stoichiometric amount of O2 is produced by the oxidation of H2O, then CO2 introduced into the gas phase is believed to be reduced by H2O to CO2RPs in the aqueous phase.

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper.

PubMed

Li, Christina W; Ciston, Jim; Kanan, Matthew W

2014-04-24

The electrochemical conversion of CO2 and H2O into liquid fuel is ideal for high-density renewable energy storage and could provide an incentive for CO2 capture. However, efficient electrocatalysts for reducing CO2 and its derivatives into a desirable fuel are not available at present. Although many catalysts can reduce CO2 to carbon monoxide (CO), liquid fuel synthesis requires that CO is reduced further, using H2O as a H(+) source. Copper (Cu) is the only known material with an appreciable CO electroreduction activity, but in bulk form its efficiency and selectivity for liquid fuel are far too low for practical use. In particular, H2O reduction to H2 outcompetes CO reduction on Cu electrodes unless extreme overpotentials are applied, at which point gaseous hydrocarbons are the major CO reduction products. Here we show that nanocrystalline Cu prepared from Cu2O ('oxide-derived Cu') produces multi-carbon oxygenates (ethanol, acetate and n-propanol) with up to 57% Faraday efficiency at modest potentials (-0.25 volts to -0.5 volts versus the reversible hydrogen electrode) in CO-saturated alkaline H2O. By comparison, when prepared by traditional vapour condensation, Cu nanoparticles with an average crystallite size similar to that of oxide-derived copper produce nearly exclusive H2 (96% Faraday efficiency) under identical conditions. Our results demonstrate the ability to change the intrinsic catalytic properties of Cu for this notoriously difficult reaction by growing interconnected nanocrystallites from the constrained environment of an oxide lattice. The selectivity for oxygenates, with ethanol as the major product, demonstrates the feasibility of a two-step conversion of CO2 to liquid fuel that could be powered by renewable electricity.

Highly uniform and monodisperse carbon nanospheres enriched with cobalt-nitrogen active sites as a potential oxygen reduction electrocatalyst

NASA Astrophysics Data System (ADS)

Wan, Xing; Wang, Hongjuan; Yu, Hao; Peng, Feng

2017-04-01

Uniform cobalt and nitrogen co-doped carbon nanospheres (CoN-CNS) with high specific surface area (865 m2 g-1) have been prepared by a simple but efficient method. The prepared CoN-CNS catalyst exhibits outstanding catalytic performance for the oxygen reduction reaction (ORR) in both alkaline and acidic electrolytes. In alkaline electrolyte, the prepared CoN-CNS has more positive half-wave potential and larger kinetic current density than commercial Pt/C. In acidic electrolyte, CoN-CNS also shows good ORR activity with high electron transfer number, its onset and half-wave potentials are all close to those of commercial carbon supported platinum catalyst (Pt/C). CoN-CNS catalyst shows more superior stability and higher methanol-tolerance than commercial Pt/C both in alkaline and in acidic electrolytes. The potassium thiocyanate-poisoning test further confirms that the cobalt-nitrogen active sites exist in CoN-CNS, which are dominating to endow high ORR catalytic activity in acidic electrolyte. This study develops a new method to prepare non-precious metal catalyst with excellent ORR performances for direct methanol fuel cells.

Understanding the contribution of non-carbon dioxide gases in deep mitigation scenarios

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

Gernaat, David; Calvin, Katherine V.; Lucas, Paul

2015-07-01

The combined 2010 emissions of methane (CH4), nitrous oxide (N2O) and the fluorinated gasses (F-gas) account for about 20-30% of total emissions and about 30% of radiative forcing. At the moment, most studies looking at reaching ambitious climate targets project the emission of carbon dioxide (CO2) to be reduced to zero (or less) by the end of the century. As for non-CO2 gases, the mitigation potential seem to be more constrained, we find that by the end of the century in the current deep mitigation scenarios non-CO2 emissions could form the lion’s share of remaining greenhouse gas emissions. In ordermore » to support effective climate policy strategies, in this paper we provide a more in-depth look at the role of non-CO2¬ emission sources (CH4, N2O and F-gases) in achieving deep mitigation targets (radiative forcing target of 2.8 W/m2 in 2100). Specifically, we look at the sectorial mitigation potential and the remaining non-CO2 emissions. By including a set of different models, we provide some insights into the associated uncertainty. Most of the remaining methane emissions in 2100 in the climate mitigation scenario come from the livestock sector. Strong reductions are seen in the energy supply sector across all models. For N2O, less reduction potential is seen compared to methane and the sectoral differences are larger between the models. The paper shows that the assumptions on remaining non-CO2 emissions are critical for the feasibility of reaching ambitious climate targets and the associated costs.« less

Reduction of CO 2 to methanol using aluminum ester FLPs

DOE PAGES

Smythe, Nathan C.; Dixon, David A.; Garner, III, Edward B.; ...

2015-10-09

Herein we report the synthesis of Al-based esters containing halogenated benzene rings. These Lewis acids were paired with phosphines to form frustrated Lewis pairs (FLPs) which could subsequently bind CO 2. While these FLPs were not sufficiently water-stable to catalyze the reduction of CO 2 to MeOH using NH 3BH 3 as the reductant, we examine the effect of varying Lewis acid strength. Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases where the acid and base are either sterically or geometrically restricted from interacting as strongly as their electronic structures would allow. This effect leads tomore » enhanced reactivity towards small molecules and, consequently, interest in their potential as metal-free catalysts [1], [2], [3], [4] and [5]. Furthermore, to-date, the biggest success has been based around the ability of a myriad of systems to heterolytically cleave H 2 and perform catalytic hydrogenations [2] and [3].« less

Tuning Product Selectivity for Aqueous CO2 Reduction with a Mn(bipyridine)-pyrene Catalyst Immobilized on a Carbon Nanotube Electrode

PubMed Central

2017-01-01

The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different intermediates were identified as responsible for the change in selectivity of the heterogenized Mn catalyst. The formation of a dimeric Mn0 species at higher surface loading was shown to preferentially lead to CO formation, whereas at lower surface loading the electrochemical generation of a monomeric Mn-hydride is suggested to greatly enhance the production of formate. These results emphasize the advantages of integrating molecular catalysts onto electrode surfaces for enhancing catalytic activity while allowing excellent control and a deeper understanding of the catalytic mechanisms. PMID:28885841

Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation.

PubMed

Rakowski DuBois, M; DuBois, Daniel L

2009-12-21

The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light-harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This Account focuses on work from our laboratories on developing molecular electrocatalysts for CO(2) reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO(2) from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox-active CO(2) carriers for concentrating CO(2). We have developed catalysts for CO(2) reduction to form CO based on a [Pd(triphosphine)(solvent)](2+) platform. Catalytic activity requires the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)](2+) units suggest that participation of a second metal in CO(2) binding may also be required for achieving very active catalysts. We also describe molecular electrocatalysts for H(2) production and oxidation based on [Ni(diphosphine)(2)](2+) complexes. Similar to palladium CO(2) reduction catalysts, these species require the optimization of both first and second coordination spheres. In this case, we use structural features of the first coordination sphere to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H(2). We use the second coordination sphere to incorporate pendant bases that assist in a number of important functions including H(2) binding, H(2) cleavage, and the transfer of protons between nickel and solution. These pendant bases, or proton relays, are likely to be important in the design of catalysts for a wide range of fuel production and fuel utilization reactions involving multiple electron and proton transfer steps. The generation of fuels from abundant substrates such as CO(2) and water remains a daunting research challenge, requiring significant advances in new inexpensive materials for light harvesting and the development of fast, stable, and efficient electrocatalysts. Although we describe progress in the development of redox-active carriers capable of concentrating CO(2) and molecular electrocatalysts for CO(2) reduction, hydrogen production, and hydrogen oxidation, much more remains to be done.

CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

DOE PAGES

Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

2015-02-07

A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

Social cost of carbon pricing of power sector CO2: accounting for leakage and other social implications from subnational policies

NASA Astrophysics Data System (ADS)

Bistline, John E.; Rose, Steven K.

2018-01-01

In environments where climate policy has partial coverage or unequal participation, carbon dioxide (CO2) emissions or economic activity may shift to locations and sectors where emissions are unregulated. This is referred to as leakage. Leakage can offset or augment emissions reductions associated with a policy, which has important environmental and economic implications. Although leakage has been studied at national levels, analysis of leakage for subnational policies is limited. This is despite greater market integration and many existing state and regional environmental regulations in the US. This study explores leakage potential, net emissions changes, and other social implications in the US energy system with regionally differentiated pricing of power sector CO2 emissions. We undertake an economic analysis using EPRI’s US-REGEN model, where power sector CO2 emissions are priced in individual US regions with a range of social cost of carbon (SCC) values. SCC estimates are being considered by policy-makers for valuing potential societal damages from CO2 emissions. In this study, we evaluate the emissions implications within the SCC pricing region, within the power sector outside the SCC region, and outside the power sector (i.e. in the rest of the energy system). Results indicate that CO2 leakage is possible within and outside the electric sector, ranging from negative 70% to over 80% in our scenarios, with primarily positive leakage outcomes. Typically ignored in policy analysis, leakage would affect CO2 reduction benefits. We also observe other potential societal effects within and across regions, such as higher electricity prices, changes in power sector investments, and overall consumption losses. Efforts to reduce leakage, such as constraining power imports into the SCC pricing region likely reduce leakage, but could also result in lower net emissions reductions, as well as larger price increases. Thus, it is important to look beyond leakage and consider a broader set of environmental and economic metrics. Leakage rates, net emissions outcomes, electricity price changes, fuel market effects, and macroeconomic costs vary by region of the country, time, policy stringency, policy design (e.g. leakage mitigation provisions), policy environment in neighboring regions, and price responsiveness of demand.

Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide

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

Abbasi, Pedram; Asadi, Mohammad; Liu, Cong

2017-01-24

Electrocatalytic conversion of carbon dioxide (CO2) into energy-rich fuels is considered to be the most efficient approach to achieve a carbon neutral cycle. Transition-metal dichalcogenides (TMDCs) have recently shown a very promising catalytic performance for CO2 reduction reaction in an ionic liquid electrolyte. Here, we report that the catalytic performance of molybdenum disulfide (MoS2), a member of TMDCs, can be significantly improved by using an appropriate dopant. Our electrochemical results indicate that 5% niobium (Nb)-doped vertically aligned MoS2 in ionic liquid exhibits 1 order of magnitude higher CO formation turnover frequency (TOF) than pristine MoS2 at an overpotential range ofmore » 50-150 mV. The TOF of this catalyst is also 2 orders of magnitude higher than that of Ag nanoparticles over the entire range of studied overpotentials (100-650 mV). Moreover, the in situ differential electrochemical mass spectrometry experiment shows the onset overpotential of 31 mV for this catalyst, which is the lowest onset potential for CO2 reduction reaction reported so far. Our density functional theory calculations reveal that low concentrations of Nb near the Mo edge atoms can enhance the TOF of CO formation by modifying the binding energies of intermediates to MoS2 edge atoms.« less

How Well Do We Know the Future of CO2 Emissions? Projecting Fleet Emissions from Light Duty Vehicle Technology Drivers.

PubMed

Martin, Niall P D; Bishop, Justin D K; Boies, Adam M

2017-03-07

While the UK has committed to reduce CO 2 emissions to 80% of 1990 levels by 2050, transport accounts for nearly a fourth of all emissions and the degree to which decarbonization can occur is highly uncertain. We present a new methodology using vehicle and powertrain parameters within a Bayesian framework to determine the impact of engineering vehicle improvements on fuel consumption and CO 2 emissions. Our results show how design changes in vehicle parameters (e.g., mass, engine size, and compression ratio) result in fuel consumption improvements from a fleet-wide mean of 5.6 L/100 km in 2014 to 3.0 L/100 km by 2030. The change in vehicle efficiency coupled with increases in vehicle numbers and fleet-wide activity result in a total fleet-wide reduction of 41 ± 10% in 2030, relative to 2012. Concerted internal combustion engine improvements result in a 48 ± 10% reduction of CO 2 emissions, while efforts to increase the number of diesel vehicles within the fleet had little additional effect. Increasing plug-in and all-electric vehicles reduced CO 2 emissions by less (42 ± 10% reduction) than concerted internal combustion engines improvements. However, if the grid decarbonizes, electric vehicles reduce emissions by 45 ± 9% with further reduction potential to 2050.

Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES.

PubMed

Doubaji, Siham; Philippe, Bertrand; Saadoune, Ismael; Gorgoi, Mihaela; Gustafsson, Torbjorn; Solhy, Abderrahim; Valvo, Mario; Rensmo, Håkan; Edström, Kristina

2016-01-08

The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah

2018-05-01

Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

Emissions reductions from expanding state-level renewable portfolio standards.

PubMed

Johnson, Jeremiah X; Novacheck, Joshua

2015-05-05

In the United States, state-level Renewable Portfolio Standards (RPS) have served as key drivers for the development of new renewable energy. This research presents a method to evaluate emissions reductions and costs attributable to new or expanded RPS programs by integrating a comprehensive economic dispatch model and a renewable project selection model. The latter model minimizes incremental RPS costs, accounting for renewable power purchase agreements (PPAs), displaced generation and capacity costs, and net changes to a state's imports and exports. We test this method on potential expansions to Michigan's RPS, evaluating target renewable penetrations of 10% (business as usual or BAU), 20%, 25%, and 40%, with varying times to completion. Relative to the BAU case, these expanded RPS policies reduce the CO2 intensity of generation by 13%, 18%, and 33% by 2035, respectively. SO2 emissions intensity decreased by 13%, 20%, and 34% for each of the three scenarios, while NOx reductions totaled 12%, 17%, and 31%, relative to the BAU case. For CO2 and NOx, absolute reductions in emissions intensity were not as large due to an increasing trend in emissions intensity in the BAU case driven by load growth. Over the study period (2015 to 2035), the absolute CO2 emissions intensity increased by 1% in the 20% RPS case and decreased by 6% and 22% for the 25% and 40% cases, respectively. Between 26% and 31% of the CO2, SO2, and NOx emissions reductions attributable to the expanded RPS occur in neighboring states, underscoring the challenges quantifying local emissions reductions from state-level energy policies with an interconnected grid. Without federal subsidies, the cost of CO2 mitigation using an RPS in Michigan is between $28 and $34/t CO2 when RPS targets are met. The optimal renewable build plan is sensitive to the capacity credit for solar but insensitive to the value for wind power.

Oxygen Generation from Carbon Dioxide for Advanced Life Support

NASA Technical Reports Server (NTRS)

Bishop, Sean; Duncan, Keith; Hagelin-Weaver, Helena; Neal, Luke; Sanchez, Jose; Paul, Heather L.; Wachsman, Eric

2007-01-01

The partial electrochemical reduction of carbon dioxide (CO2) using ceramic oxygen generators (COGs) is well known and widely studied. However, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight for life support if the oxygen can be recovered. Recently, the University of Florida devel- oped novel ceramic oxygen generators employing a bilayer elec- trolyte of gadolinia-doped ceria and erbia-stabilized bismuth ox- ide (ESB) for NASA's future exploration of Mars. The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. The strategy discussed here for advanced life support systems employs a catalytic layer com- bined with a COG cell so that CO2 is reduced all the way to solid carbon and oxygen without carbon buildup on the COG cell and subsequent deactivation.

Ceria-based electrospun fibers for renewable fuel production via two-step thermal redox cycles for carbon dioxide splitting.

PubMed

Gibbons, William T; Venstrom, Luke J; De Smith, Robert M; Davidson, Jane H; Jackson, Gregory S

2014-07-21

Zirconium-doped ceria (Ce(1-x)Zr(x)O2) was synthesized through a controlled electrospinning process as a promising approach to cost-effective, sinter-resistant material structures for high-temperature, solar-driven thermochemical redox cycles. To approximate a two-step redox cycle for solar fuel production, fibrous Ce(1-x)Zr(x)O2 with relatively low levels of Zr-doping (0 < x < 0.1) were cycled in an infrared-imaging furnace with high-temperature (up to 1500 °C) partial reduction and lower-temperature (∼800 °C) reoxidation via CO2 splitting to produce CO. Increases in Zr content improve reducibility and sintering resistance, and, for x≤ 0.05, do not significantly slow reoxidation kinetics for CO production. Cycle stability of the fibrous Ce(1-x)Zr(x)O2 (with x = 0.025) was assessed for a range of conditions by measuring rates of O2 release during reduction and CO production during reoxidation and by assessing post-cycling fiber crystallite sizes and surface areas. Sintering increases with reduction temperature but occurs primarily along the fiber axes. Even after 108 redox cycles with reduction at 1400 °C and oxidation with CO2 at 800 °C, the fibers maintain their structure with surface areas of ∼0.3 m(2) g(-1), higher than those observed in the literature for other ceria-based structures operating at similarly high temperature conditions. Total CO production and peak production rate stabilize above 3.0 mL g(-1) and 13.0 mL min(-1) g(-1), respectively. The results show the potential for electrospun oxides as sinter-resistant material structures with adequate surface area to support rapid CO2 splitting in solar thermochemical redox cycles.

Sol-gel Synthesis, Photo- and Electrocatalytic Properties of Mesoporous TiO2 Modified with Transition Metal Ions

NASA Astrophysics Data System (ADS)

Smirnova, N.; Petrik, I.; Vorobets, V.; Kolbasov, G.; Eremenko, A.

2017-03-01

Mesoporous nanosized titania films modified with Co2+, Ni2+, Mn3+, and Cu2+ ions have been produced by templated sol-gel method and characterized by optical spectroscopy, X-ray diffraction (XRD), and Brunauer, Emmett, and Teller (BET) surface area measurement. Band gap energy and the position of flat band potentials were estimated by photoelectrochemical measurements. The films doped with transition metals possessed higher photocurrent quantum yield, as well as photo- and electrochemical activity compared to undoped samples. Mn+/TiO2 (M-Co, Ni, Mn, Cu) electrodes with low dopant content demonstrate high efficiency in electrocatalytic reduction of dissolved oxygen. Polarization curves of TiO2, TiO2/Ni2+, TiO2/Co2+/3+, and TiO2/Mn3+ electrodes contain only one current wave (oxygen reduction current). It means that reaction proceeds without the formation of an intermediate product H2O2.

Rate Controlling Step in the Reduction of Iron Oxides; Kinetics and Mechanism of Wüstite-Iron Step in H2, CO and H2/CO Gas Mixtures

NASA Astrophysics Data System (ADS)

El-Geassy, Abdel-Hady A.

2017-09-01

Wüstite (W1 and W2) micropellets (150-50 μm) were prepared from the reduction of pure Fe2O3 and 2.1% SiO2-doped Fe2O3 in 40%CO/CO2 gas mixture at 1000°C which were then isothermally reduced in H2, CO and H2/CO gas mixtures at 900-1100°C. The reduction reactions was followed by Thermogravimetric Analysis (TG) technique. The effect of gas composition, gas pressure and temperature on the rate of reduction was investigated. The different phases formed during the reduction were chemically and physically characterized. In SiO2-doped wüstite, fayalite (Fe2SiO3) was identified. At the initial reduction stages, the highest rate was obtained in H2 and the lowest was in CO gas. In H2/CO gas mixtures, the measured rate did not follow a simple additive equation. The addition of 5% H2 to CO led to a measurable increase in the rate of reduction compared with that in pure CO. Incubation periods were observed at the early reduction stages of W1 in CO at lower gas pressure (<0.25 atm). In SiO2-doped wüstite, reaction rate minimum was detected in H2 and H2-rich gas mixtures at 925-950°C. The influence of addition of H2 to CO or CO to H2 on the reduction reactions, nucleation and grain growth of iron was intensively studied. Unlike in pure wüstite, the presence of fayalite enhances the reduction reactions with CO and CO-rich gas mixtures. The chemical reaction equations of pure wüstite with CO are given showing the formation of carbonyl-like compound [Fem(CO2)n]*. The apparent activation energy values, at the initial stages, ranged from 53.75 to 133.97 kJ/mole indicating different reaction mechanism although the reduction was designed to proceed by the interfacial chemical reaction.

Membraneless laminar flow cell for electrocatalytic CO2 reduction with liquid product separation

NASA Astrophysics Data System (ADS)

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei; Ager, Joel W.

2017-04-01

The production of liquid fuel products via electrochemical reduction of CO2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O2) from reaching the cathode. Ion-conducting membranes have been applied in CO2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flow cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.

Cement replacement by sugar cane bagasse ash: CO2 emissions reduction and potential for carbon credits.

PubMed

Fairbairn, Eduardo M R; Americano, Branca B; Cordeiro, Guilherme C; Paula, Thiago P; Toledo Filho, Romildo D; Silvoso, Marcos M

2010-09-01

This paper presents a study of cement replacement by sugar cane bagasse ash (SCBA) in industrial scale aiming to reduce the CO(2) emissions into the atmosphere. SCBA is a by-product of the sugar/ethanol agro-industry abundantly available in some regions of the world and has cementitious properties indicating that it can be used together with cement. Recent comprehensive research developed at the Federal University of Rio de Janeiro/Brazil has demonstrated that SCBA maintains, or even improves, the mechanical and durability properties of cement-based materials such as mortars and concretes. Brazil is the world's largest sugar cane producer and being a developing country can claim carbon credits. A simulation was carried out to estimate the potential of CO(2) emission reductions and the viability to issue certified emission reduction (CER) credits. The simulation was developed within the framework of the methodology established by the United Nations Framework Convention on Climate Change (UNFCCC) for the Clean Development Mechanism (CDM). The State of São Paulo (Brazil) was chosen for this case study because it concentrates about 60% of the national sugar cane and ash production together with an important concentration of cement factories. Since one of the key variables to estimate the CO(2) emissions is the average distance between sugar cane/ethanol factories and the cement plants, a genetic algorithm was developed to solve this optimization problem. The results indicated that SCBA blended cement reduces CO(2) emissions, which qualifies this product for CDM projects. 2010 Elsevier Ltd. All rights reserved.

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

Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO 2 reduction ability. We reported complexes are of the type Re(N-N)(CO) 3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO 2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO 2 reduction by 1 in acetonitrile using densitymore » functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG ‡ = 27.2 kcal mol –1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO) 3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (i cat/i p) 2, up to 7 times larger than that of I.« less

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

Comparisons of MN2S2vs. bipyridine as redox-active ligands to manganese and rhenium in (L-L)M'(CO)3Cl complexes.

PubMed

Lunsford, Allen M; Goldstein, Kristina F; Cohan, Matthew A; Denny, Jason A; Bhuvanesh, Nattamai; Ding, Shengda; Hall, Michael B; Darensbourg, Marcetta Y

2017-04-19

The bipyridine ligand is renowned as a photo- and redox-active ligand in catalysis; the latter has been particularly explored in the complex Re(bipy)(CO) 3 Cl for CO 2 reduction. We ask whether a bidentate, redox-active MN 2 S 2 metallodithiolate ligand in heterobimetallic complexes of Mn and Re might similarly serve as a receptor and conduit of electrons. In order to assess the electrochemical features of such designed bimetallics, a series of complexes featuring redox active MN 2 S 2 metallodithiolates, with M = Ni 2+ , {Fe(NO)} 2+ , and {Co(NO)} 2+ , bound to M'(CO) 3 X, where M' = Mn and Re, were synthesized and characterized using IR and EPR spectroscopies, X-ray diffraction, cyclic voltammetry, and density functional theory (DFT) computations. Butterfly type structures resulted from binding of the convergent lone pairs of the cis-sulfur atoms to the M'(CO) 3 X unit. Bond distances and angles are similar across the M' metal series regardless of the ligand attached. Electrochemical characterizations of [MN 2 S 2 ·Re(CO) 3 Cl] showed the redox potential of the Re is significantly altered by the identity of the metal in the N 2 S 2 pocket. DFT calculations proved useful to identify the roles played by the MN 2 S 2 ligands, upon reduction of the bimetallics, in altering the lability of the Re-Cl bond and the ensuing effect on the reduction of Re I to Re 0 .

Active-site models for the nickel-iron hydrogenases: effects of ligands on reactivity and catalytic properties.

PubMed

Carroll, Maria E; Barton, Bryan E; Gray, Danielle L; Mack, Amanda E; Rauchfuss, Thomas B

2011-10-03

Described are new derivatives of the type [HNiFe(SR)(2)(diphosphine)(CO)(3)](+), which feature a Ni(diphosphine) group linked to a Fe(CO)(3) group by two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)(3)](+) ([1H](+)) and its activity as a catalyst for the reduction of protons (J. Am. Chem. Soc. 2010, 132, 14877). Work described in this paper focuses on the effects on properties of NiFe model complexes of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)(2)(diphosphine) with FeI(2)(CO)(4) followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via a metastable μ-iodo derivative. Attempted isolation of such species led to the crystallization of NiFe(Me(2)pdt)(dppe)I(2), which features tetrahedral Fe(II) and square planar Ni(II) centers (H(2)Me(2)pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)(3) (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)(3) (3), and NiFe(edt)(dcpe)(CO)(3) (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI(2)(CO)(4) + Ni(SPh)(2)(dppe) route gave the tetrametallic species [(CO)(2)Fe(SPh)(2)Ni(CO)](2)(μ-dppe)(2). Crystallographic analysis of the edt-dcpe compund [2H]BF(4) and the edt-dppe compound [3H]BF(4) verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [3H]BF(4) we prepared the PPh(3) derivative [HNiFe(edt)(dppe)(PPh(3))(CO)(2)]BF(4) ([5H]BF(4)), which was obtained as a ∼2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) (dppe = Ph(2)PCH(2)CH(2)PPh(2)) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pK(a)(PhCN) units, from ∼11 to ∼13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2](0/+) couple occurs at E(1/2) = -820 for [2](0/+) vs -574 mV (vs Fc(+/0)) for [1](0/+). Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH(2)ClCO(2)H by [2H](+) is about 50 s(-1) (25 °C), twice that of [1H](+). The edt-dppe complex [2H](+) proved to be the most active catalyst, with an acid-independent rate of 300 s(-1).

Selective CO{sub 2} reduction conjugated with H{sub 2}O oxidation utilizing semiconductor/metal-complex hybrid photocatalysts

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

Morikawa, T., E-mail: morikawa@mosk.tytlabs.co.jp; Sato, S., E-mail: morikawa@mosk.tytlabs.co.jp; Arai, T., E-mail: morikawa@mosk.tytlabs.co.jp

2013-12-10

We developed a new hybrid photocatalyst for CO{sub 2} reduction, which is composed of a semiconductor and a metal complex. In the hybrid photocatalyst, ΔG between the position of conduction band minimum (E{sub CBM}) of the semiconductor and the CO{sub 2} reduction potential of the complex is an essential factor for realizing fast electron transfer from the conduction band of semiconductor to metal complex leading to high photocatalytic activity. On the basis of this concept, the hybrid photocatalyst InP/Ru-complex, which functions in aqueous media, was developed. The photoreduction of CO{sub 2} to formate using water as an electron donor andmore » a proton source was successfully achieved as a Z-scheme system by functionally conjugating the InP/Ru-complex photocatalyst for CO{sub 2} reduction with a TiO{sub 2} photocatalyst for water oxidation. The conversion efficiency from solar energy to chemical energy was ca. 0.04%, which approaches that for photosynthesis in a plant. Because this system can be applied to many other inorganic semiconductors and metal-complex catalysts, the efficiency and reaction selectivity can be enhanced by optimization of the electron transfer process including the energy-band configurations, conjugation conformations, and catalyst structures. This electrical-bias-free reaction is a huge leap forward for future practical applications of artificial photosynthesis under solar irradiation to produce organic species.« less

Isotopic Probe Illuminates the Role of the Electrode Surface in Proton Coupled Hydride Transfer Electrochemical Reduction of Pyridinium on Pt(111)

DOE PAGES

Zeitler, Elizabeth L.; Ertem, Mehmed Z.; Pander, III, James E.; ...

2015-10-21

A recently proposed mechanism for electrochemical CO 2 reduction on Pt (111) catalyzed by aqueous acidic pyridine solutions suggests that the observed redox potential of ca. -600 mV vs. SCE is due to the one-electron reduction of pyridinium through proton coupled electron transfer (PCET) to form H atoms adsorbed on the Pt surface (H ads). The initial pyridinium reduction was probed isotopically via deuterium substitution. A combined experimental and theoretical analysis found equilibrium isotope effects (EIE) due to deuterium substitution at the acidic pyridinium site. A shift in the cathodic cyclic voltammetric half wave potential of -25 mV was observed,more » consistent with the theoretical prediction of -40 mV based on the recently proposed reaction mechanism where pyridinium is essential to establish a high concentration of Bronsted acid in contact with the substrate CO 2 and with the Pt surface. A prefeature in the cyclic voltammogram was examined under isotopic substitution and indicated an H-ads intermediate in pyridinium reduction. In conclusion, the theoretical prediction and observation of an BM supported the assignment of the cathodic wave to the proposed reduction of pyridinium through PCET forming H ads and eventually H 2 on the Pt surface.« less

Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO 2 reduction

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

Jiang, Kun; Sandberg, Robert B.; Akey, Austin J.

Here, electrocatalytic CO 2 reduction to higher-value hydrocarbons beyond C 1 products is desirable for applications in energy storage, transportation and the chemical industry. Cu catalysts have shown the potential to catalyse C–C coupling for C 2+ products, but still suffer from low selectivity in water. Here, we use density functional theory to determine the energetics of the initial C–C coupling steps on different Cu facets in CO 2 reduction, and suggest that the Cu(100) and stepped (211) facets favour C 2+ product formation over Cu(111). To demonstrate this, we report the tuning of facet exposure on Cu foil throughmore » the metal ion battery cycling method. Compared with the polished Cu foil, our 100-cycled Cu nanocube catalyst with exposed (100) facets presents a sixfold improvement in C 2+ to C 1 product ratio, with a highest C 2+ Faradaic efficiency of over 60% and H 2 below 20%, and a corresponding C 2+ current of more than 40 mA cm –2.« less

Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO 2 reduction

DOE PAGES

Jiang, Kun; Sandberg, Robert B.; Akey, Austin J.; ...

2018-01-15

Here, electrocatalytic CO 2 reduction to higher-value hydrocarbons beyond C 1 products is desirable for applications in energy storage, transportation and the chemical industry. Cu catalysts have shown the potential to catalyse C–C coupling for C 2+ products, but still suffer from low selectivity in water. Here, we use density functional theory to determine the energetics of the initial C–C coupling steps on different Cu facets in CO 2 reduction, and suggest that the Cu(100) and stepped (211) facets favour C 2+ product formation over Cu(111). To demonstrate this, we report the tuning of facet exposure on Cu foil throughmore » the metal ion battery cycling method. Compared with the polished Cu foil, our 100-cycled Cu nanocube catalyst with exposed (100) facets presents a sixfold improvement in C 2+ to C 1 product ratio, with a highest C 2+ Faradaic efficiency of over 60% and H 2 below 20%, and a corresponding C 2+ current of more than 40 mA cm –2.« less

CO-CO coupling on Cu facets: Coverage, strain and field effects

DOE PAGES

Sandberg, Robert B.; Montoya, Joseph H.; Chan, Karen; ...

2016-08-21

We present a DFT study on the effect of coverage, strain, and electric field on CO-CO coupling energetics on Cu (100), (111), and (211). Our calculations indicate that CO-CO coupling is facile on all three facets in the presence of a cation-induced electric field in the Helmholtz plane, with the lowest barrier on Cu(100). The CO dimerization pathway is therefore expected to play a role in C 2 formation at potentials negative of the Cu potential of zero charge, corresponding to CO 2/CO reduction conditions at high pH. Both increased *CO coverage and tensile strain further improve C-C coupling energeticsmore » on Cu (111) and (211). Since CO dimerization is facile on all 3 Cu facets, subsequent surface hydrogenation steps may also play an important role in determining the overall activity towards C 2 products. Adsorption of *CO, *H, and *OH on the 3 facets were investigated with a Pourbaix analysis. Here, the (211) facet has the largest propensity to co-adsorb *CO and *H, which would favor surface hydrogenation following CO dimerization.« less

Examining ruthenium chromophores for the photochemical reduction of CO2 to methanol

NASA Astrophysics Data System (ADS)

Boston, David J.

Our consumption of energy for transportation and electricity has been growing as quickly as our population. As this demand for energy increases we increase our production of carbon dioxide by the burning of fossil fuels to try and meet this increasing demand. A sustainable method to convert carbon dioxide (CO2) to a viable liquid fuel is one potential way in which both the increasing energy demand and increasing CO2 concentration issues can both be helped. Currently such methods being investigated include thermal, electrochemical, and photochemical processes. Because thermal conversion is not an ideal situation because of the requirement of strong reducing agents or extreme conditions such as steam reformation reactions, we need to find better alternatives such as electrochemical and photochemical methods. Both electrochemical and photochemical methods have the ability to be sustainable, however, the vast majority of these systems are limited to producing CO and/or formic acid, with only a few performing deeper reduction to products such formaldehyde, methanol and methane. All of the systems capable of reducing CO2 past two electrons involve either a heterogeneous catalyst (e.g. TiO2) or an electrode. In recent times Bocarsly and coworkers have shown that pyridine was capable of reducing CO2 to methanol through a sequential process of proton and electron transfers. This process seems to start with the formation of a CO2-pyridine adduct in solution that is reduced one more time to form formate/formic acid. The next reduction is a slow process and allows for a buildup of formate in solution leading to a higher formate concentration in solution. The subsequent reductions seem to occur very rapidly and form methanol at good efficiencies. Theoretical work done recently has argued for the necessity of the Pt, Pd, or GaP surface in the electrochemistry. Carter and coworkers have claimed that the surface of the electrode is a necessary part of the catalysis with the pyridinium being only a cocatalyst for the reduction of CO2. However, Musgrave and coworkers predict that the homogeneous reductions can take place with the aid of water molecules in solution. They allow for a PCET process to take place between the CO 2 and the pyridinium radical. This would allow for a second pathway for the catalytic reduction of CO2 to methanol. Work done during this dissertation has shown that the photochemical reduction of carbon dioxide to methanol is possible using pyridine in a similar manner to Bocarsly and coworkers in their electrochemical system. By replacing the electrode with Ru(phen)3Cl2 it is still possible to drive the reaction using excited states of the chromophore to provide the electrons with enough energy to reduce the pyridinium to the radical species. This system has been shown to produce up to 66 BM methanol after 6 hours of irradiation of 470 nm light. Production of formate is also observed, with ~27 mM being observed within the first hour of irradiation. This system was further investigated with the incorporation of the pyridine catalyst into a chromophore system using the complex [Ru(phen)2dppz](PF 6)2, [Ru(phen)2pbtpalpha](PF6) 2, and [Ru(phen)2pbtpbeta](PF6)2. Cyclic voltammetry experiments for these complexes show similar reduction potentials for with ~100 mV difference between them with [Ru(phen)2dppz](PF 6)2 being the most negative and [Ru(phen)2pbtpbeta](PF 6)2 being the most positive. When the electrolyte solution was saturated with CO2 only [Ru(phen)2pbtpalpha](PF 6)2 and [Ru(phen)2pbtpbeta](PF6) 2 showed a response signifying catalysis was taking place. Initial photochemical tests with these complexes showed that [Ru(phen)2pbtpalpha](PF 6)2 seemed to undergo dimer formation in the absence of CO 2 with [Ru(phen)2pbtpbeta](PF6)2 forming a singly reduced species that is oxidized upon introduction of additional CO2. Electrolysis of [Ru(phen)2pbtpbeta](PF6 )2 produces ~900 BM methanol with both CO and formate being produced as well. Photolysis of [Ru(phen)2pbtpbeta](PF6 )2 in DMF with 1 M H2O and 0.1M TEA, no CO formation observed, however, both methanol and formic acid were observed after 1 hours of irradiation with methanol reaching 45 BM, 285 microM formaldehyde and 650 microM formate.

Active-Site Models for the Nickel-Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties

PubMed Central

Carroll, Maria E.; Barton, Bryan E.; Gray, Danielle L.; Mack, Amanda E.; Rauchfuss, Thomas B.

2011-01-01

Described are new derivatives of the type [HNiFe(SR)2(diphosphine)(CO)3]+, which feature a Ni(diphosphine) group linked to a Fe(CO)3 group via two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)3]+ ([1H]+) and its activity as a catalyst for the reduction of protons. Work described in this paper focused on the effects of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)2(diphosphine) with FeI2(CO)4 followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via metastable μ-iodo derivatives. Attempted isolation of such species led to the crystallization of NiFe(Me2pdt)(dppe)I2, which features tetrahedral Fe(II) and square planar Ni(II) centers (Me2pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)3 (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)3 (3), and NiFe(edt)(dcpe)(CO)3 (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI2(CO)4 + Ni(SPh)2(dppe) route gave the tetrametallic species [(CO)2Fe(SPh)2Ni(CO)]2(μ-dppe)2. Crystallographic analysis of the edt-dcpe compund [2H]BF4 and the edt-dppe compound [3H]BF4 verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [4H]BF4 we prepared the PPh3 derivative [HNiFe(edt)(dppe)(PPh3)(CO)2]BF4 ([5H]BF4), which was obtained as a ~2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pKaMeCN units, from ~11 to ~13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2]0/+ couple occurs at E1/2 = −820 for [2]0/+ vs −574 mV (vs Fc+/0) for [1]0/+. Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH2ClCO2H by [2H]+ is ca. 50 s−1 (25 °C), twice that of [1H]+. The edt-dppe complex [2H]+ proved to be the most active catalyst, with an acid-independent rate of 300 s−1. PMID:21866886

Methanogenesis-induced pH–Eh shifts drives aqueous metal(loid) mobility in sulfide mineral systems under CO2 enriched conditions

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

Harvey, Omar R.; Qafoku, Nikolla; Cantrell, Kirk J.

2016-01-15

Accounting for microbially-mediated CO2 transformation is pivotal to assessing geochemical implications for elevated CO2 in subsurface environments. A series of batch-reactor experiments were conducted to decipher links between autotrophic methanogenesis, CO2 dynamics and aqueous Fe, As and Pb concentrations in the presence of sulfide minerals. Microbially-mediated solubility-trapping followed by pseudo-first order reduction of HCO3- to CH4 (k’ = 0.28-0.59 d-1) accounted for 95% of the CO2 loss from methanogenic experiments. Bicarbonate-to-methane reduction was pivotal in the mitigation of CO2-induced acidity (~1 pH unit) and enhancement of reducing conditions (Eh change from -0.215 to -0.332V ). Methanogenesis-associated shifts in pH-Eh valuesmore » showed no significant effect on aqueous Pb but favored, 1) increased aqueous As as a result of microbially-mediated dissolution of arsenopyrite and 2) decreased aqueous Fe due to mineral-trapping of CO2-mobilized Fe as Fe-carbonate. Its order of occurrence (and magnitude), relative to solubility- and mineral-trapping, highlighted the potential for autotrophic methanogenesis to modulate both carbon sequestration and contaminant mobility in CO2-impacted subsurface environments.« less

Electrodeposition of germanium from supercritical fluids.

PubMed

Ke, Jie; Bartlett, Philip N; Cook, David; Easun, Timothy L; George, Michael W; Levason, William; Reid, Gillian; Smith, David; Su, Wenta; Zhang, Wenjian

2012-01-28

Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.

Impacts of potential CO2-reduction policies on air quality in the United States.

PubMed

Trail, Marcus A; Tsimpidi, Alexandra P; Liu, Peng; Tsigaridis, Kostas; Hu, Yongtao; Rudokas, Jason R; Miller, Paul J; Nenes, Athanasios; Russell, Armistead G

2015-04-21

Impacts of emissions changes from four potential U.S. CO2 emission reduction policies on 2050 air quality are analyzed using the community multiscale air quality model (CMAQ). Future meteorology was downscaled from the Goddard Institute for Space Studies (GISS) ModelE General Circulation Model (GCM) to the regional scale using the Weather Research Forecasting (WRF) model. We use emissions growth factors from the EPAUS9r MARKAL model to project emissions inventories for two climate tax scenarios, a combined transportation and energy scenario, a biomass energy scenario and a reference case. Implementation of a relatively aggressive carbon tax leads to improved PM2.5 air quality compared to the reference case as incentives increase for facilities to install flue-gas desulfurization (FGD) and carbon capture and sequestration (CCS) technologies. However, less capital is available to install NOX reduction technologies, resulting in an O3 increase. A policy aimed at reducing CO2 from the transportation sector and electricity production sectors leads to reduced emissions of mobile source NOX, thus reducing O3. Over most of the U.S., this scenario leads to reduced PM2.5 concentrations. However, increased primary PM2.5 emissions associated with fuel switching in the residential and industrial sectors leads to increased organic matter (OM) and PM2.5 in some cities.

Carbon dioxide recycling: emerging large-scale technologies with industrial potential.

PubMed

Quadrelli, Elsje Alessandra; Centi, Gabriele; Duplan, Jean-Luc; Perathoner, Siglinda

2011-09-19

This Review introduces this special issue of ChemSusChem dedicated to CO(2) recycling. Its aim is to offer an up-to-date overview of CO(2) chemical utilization (inorganic mineralization, organic carboxylation, reduction reactions, and biochemical conversion), as a continuation and extension of earlier books and reviews on this topic, but with a specific focus on large-volume routes and projects/pilot plants that are currently emerging at (pre-)industrial level. The Review also highlights how some of these routes will offer a valuable opportunity to introduce renewable energy into the existing energy and chemical infrastructure (i.e., "drop-in" renewable energy) by synthesis of chemicals from CO(2) that are easy to transport and store. CO(2) conversion therefore has the potential to become a key pillar of the sustainable and resource-efficient production of chemicals and energy from renewables. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An impact assessment of sustainable technologies for the Chinese urban residential sector at provincial level

NASA Astrophysics Data System (ADS)

Xing, Rui; Hanaoka, Tatsuya; Kanamori, Yuko; Dai, Hancheng; Masui, Toshihiko

2015-06-01

Recently, energy use in the urban residential sector of China has drastically increased due to higher incomes and urbanization. The fossil fuels dominant energy supply has since worsened the air quality, especially in urban areas. In this study we estimate the future energy service demands in Chinese urban residential areas, and then use an AIM/Enduse model to evaluate the emission reduction potential of CO2, SO2, NOx and PM. Considering the climate diversity and its impact on household energy service demands, our analysis is down-scaled to the provincial-level. The results show that in most of the regions, penetration of efficient technologies will bring CO2 emission reductions of over 20% compared to the baseline by the year 2030. Deployment of energy efficient technologies also co-benefits GHG emission reduction. However, efficient technology selection appears to differ across provinces due to climatic variation and economic disparity. For instance, geothermal heating technology is effective for the cold Northern areas while biomass technology contributes to emission reduction the most in the warm Southern areas.

Microbial mineralization of ethene under sulfate-reducing conditions

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.

2002-01-01

A limited investigation of the potential for anaerobic ethylene biodegradation under SO4-reducing conditions was performed. Microorganisms indigenous to a lake-bed sediment completely mineralized [1,2-14C] ethylene to 14CO2 when incubated under SO4-reducing conditions. Reliance on ethylene and/or ethane accumulation as a quantitative indicator of complete reductive dechlorination of chloroethylene contaminants may not be warranted. SO4 addition stimulated SO4 reduction as indicated by decreasing SO4 concentrations (> 40% decrease) and production of dissolved sulfide (880 ??M). SO4 amendment completely suppressed the production of ethane and methane. The concomitant absence of ethane and methane production under SO4-amended conditions was consistent with previous conclusions that reduction of ethylene to ethane occurred under methanogenic conditions. A lack of ethylene accumulation under SO4-reducing conditions may reflect insignificant reductive dechlorination of vinyl chloride or efficient anaerobic mineralization of ethylene to CO2.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid

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

Asadi, M.; Kim, K.; Liu, C.

2016-07-28

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform thatmore » concurrently oxidized water in the absence of any external potential.« less

A promising approach for the recovery of high value-added metals from spent lithium-ion batteries

NASA Astrophysics Data System (ADS)

Hu, Juntao; Zhang, Jialiang; Li, Hongxu; Chen, Yongqiang; Wang, Chengyan

2017-05-01

The aim of the paper is to present a promising approach for recycling high value-added metals from the cathode materials of spent LIBs. The synthesis process of NCM cathode material enlightened us to apply reduction roasting to break LiNixCoyMnzO2 into simple compounds or metals. Accordingly, the effect of several factors such as temperature, carbon dosage and roasting time is assessed on the leaching efficiency of valuable metals. The roasted products are analyzed by XRD and SEM-EDS, and the results show that the cathode material after reduction roasting is primarily transformed into Li2CO3, Ni, Co and MnO. However, the solubility of Li2CO3 is relatively low, so carbonated water leaching is used to treat the roasted products. Then the filtrate is evaporated for the preparation of pure Li2CO3, and residue is leached to recycle other metals with H2SO4. The results indicate that, after roasted at 650 °C for 3 h with 19.9% carbon dosage, 84.7% Li is preferentially recovered via carbonated water leaching, and more than 99% Ni, Co and Mn are recycled via acid leaching without adding reductant. Finally, the products of Li2CO3, NiSO4, CoSO4 and MnSO4 are obtained. The process have great potential for industrial-scale recycling from spent LIBs.

Reducing CO2 Emissions through Lightweight Design and Manufacturing

NASA Astrophysics Data System (ADS)

Carruth, Mark A.; Allwood, Julian M.; Milford, Rachel L.

2011-05-01

To meet targeted 50% reductions in industrial CO2 emissions by 2050, demand for steel and aluminium must be cut. Many steel and aluminium products include redundant material, and the manufacturing routes to produce them use more material than is necessary. Lightweight design and optimized manufacturing processes offer a means of demand reduction, whilst creating products to perform the same service as existing ones. This paper examines two strategies for demand reduction: lightweight product design; and minimizing yield losses through the product supply chain. Possible mass savings are estimated for specific case-studies on metal-intensive products, such as I-beams and food cans. These estimates are then extrapolated to other sectors to produce a global estimate for possible demand reductions. Results show that lightweight product design may offer potential mass savings of up to 30% for some products, whilst yield in the production of others could be improved by over 20%. If these two strategies could be combined for all products, global demand for steel and aluminium would be reduced by nearly 50%. The impact of demand reduction on CO2 emissions is presented, and barriers to the adoption of new, lightweight technologies are discussed.

Attempts To Catalyze the Electrochemical CO2-to-Methanol Conversion by Biomimetic 2e(-) + 2H(+) Transferring Molecules.

PubMed

Saveant, Jean-Michel; Tard, Cédric

2016-01-27

In the context of the electrochemical and photochemical conversion of CO2 to liquid fuels, one of the most important issues of contemporary energy and environmental issues, the possibility of pushing the reduction beyond the CO and formate level and catalytically generate products such as methanol is particularly attractive. Biomimetic 2e(-) + 2H(+) is often viewed as a potential hydride donor. This has been the object of a recent interesting attempt (J. Am. Chem. Soc. 2014, 136, 14007) in which 6,7-dimethyl-4-hydroxy-2-mercaptopteridine was reported as a catalyst of the electrochemical conversion of CO2 to methanol and formate, based on cyclic voltammetric, (13)C NMR, IR, and GC analyses. After checking electrolysis at the reported potential and at a more negative potential to speed up the reaction, it appears, on (1)H NMR and gas chromatographic grounds, that there is neither catalysis nor methanol and nor formate production. (1)H NMR (with H2O presaturation) brings about an unambiguous answer to the eventual production of methanol and formate, much more so than (13)C NMR, which can even be misleading when no internal standard is used as in the above-mentioned paper. IR analysis is even less conclusive. Use of a GC technique with sufficient sensitivity confirmed the lack of methanol formation. The direct or indirect hydride transfer electrochemical reduction of CO2 to formate and to methanol remains an open question. Original ideas and efforts such as those discussed here are certainly worth tempting. However, in view of the importance of the stakes, it appears necessary to carefully check reports in this area.

Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

NASA Astrophysics Data System (ADS)

Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

2018-02-01

Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

Bimetallic core-based cuboctahedral core-shell nanoclusters for the formation of hydrogen peroxide (2e- reduction) over water (4e- reduction): role of core metals.

PubMed

Mahata, Arup; Pathak, Biswarup

2017-07-13

The design of an efficient and selective catalyst for hydrogen peroxide (H 2 O 2 ) formation is highly sought due to its industrial importance. As alternatives to a conventional Pd-Au alloy-based catalyst, three cuboctahedral core-shell nanoclusters (Au 19 @Pt 60 , Co 19 @Pt 60 and Au 10 Co 9 @Pt 60 NCs) have been investigated. Their catalytic activities toward H 2 O 2 formation have been compared with that of pure Pt cuboctahedral NC (Pt 79 ). Much attention has been devoted to thermodynamic and kinetic parameters to find out the feasibility of the two-electron (2e - ) over the four-electron (4e - ) oxygen reduction reaction (ORR) to improve the product selectivity (H 2 O vs. H 2 O 2 ). Elementary steps corresponding to H 2 O 2 formation are significantly improved over the Au 10 Co 9 @Pt 60 NC catalyst compared with the pure core-shell NCs and periodic surface based catalysts. Furthermore, the Au 10 Co 9 @Pt 60 NC favours H 2 O 2 formation via the much desired Langmuir-Hinshelwood mechanism. The potential-dependent study shows that the H 2 O 2 formation is thermodynamically favourable up to 0.43 V on the Au 10 Co 9 @Pt 60 NC and thus the overpotential for the 2e - ORR process is significantly lowered. Besides, the Au 10 Co 9 @Pt 60 NC is highly selective for H 2 O 2 formation over H 2 O formation.

Development of a Next-Generation Membrane-Integrated Adsorption Processor for CO2 Removal and Compression for Closed-Loop Air Revitalization Systems

NASA Technical Reports Server (NTRS)

Mulloth, Lila; LeVan, Douglas

2002-01-01

The current CO2 removal technology of NASA is very energy intensive and contains many non-optimized subsystems. This paper discusses the concept of a next-generation, membrane integrated, adsorption processor for CO2 removal nd compression in closed-loop air revitalization systems. This processor will use many times less power than NASA's current CO2 removal technology and will be capable of maintaining a lower CO2 concentration in the cabin than that can be achieved by the existing CO2 removal systems. The compact, consolidated, configuration of gas dryer, CO2 separator, and CO2 compressor will allow continuous recycling of humid air in the cabin and supply of compressed CO2 to the reduction unit for oxygen recovery. The device has potential application to the International Space Station and future, long duration, transit, and planetary missions.

Role of heteroatoms in S, N-codoped nanoporous carbons in CO2 (photo)electrochemical reduction.

PubMed

Bandosz, Teresa; Li, Wanlu

2018-06-19

Thiourea-modified wood-based activated carbons were evaluated as catalysts for CO2 electrochemical reduction reaction (CO2ERR). The materials obtained at 950oC showed a long stability. The results indicated that thiophenic sulfur provides catalytic activity for CO formation. However, it was not as active for CH4 formation as was pyridinic-N. Tafel plots suggested that the nanoporous structure enhanced the kinetics for CO2 reduction. The electric conductivity limited the activity for CO2ERR in the materials modified at 600, 800 and 900oC. The effect of visible light on CO2ERR was also investigated in this study. Upon irradiation, photocurrent was generated, and a current density increased during CO2 reduction process. Combined with a band-gap alignment, the results indicate that thiophenic-S in the carbon matrix contributed to sample's photoactivity in visible light. These species enhance the overall reduction process promoting both hydrogen evolution reaction and CO2 reduction to CO. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flavin-Based Electron Bifurcation, Ferredoxin, Flavodoxin, and Anaerobic Respiration With Protons (Ech) or NAD+ (Rnf) as Electron Acceptors: A Historical Review

PubMed Central

Buckel, Wolfgang; Thauer, Rudolf K.

2018-01-01

Flavin-based electron bifurcation is a newly discovered mechanism, by which a hydride electron pair from NAD(P)H, coenzyme F420H2, H2, or formate is split by flavoproteins into one-electron with a more negative reduction potential and one with a more positive reduction potential than that of the electron pair. Via this mechanism microorganisms generate low- potential electrons for the reduction of ferredoxins (Fd) and flavodoxins (Fld). The first example was described in 2008 when it was found that the butyryl-CoA dehydrogenase-electron-transferring flavoprotein complex (Bcd-EtfAB) of Clostridium kluyveri couples the endergonic reduction of ferredoxin (E0′ = −420 mV) with NADH (−320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (−10 mV) with NADH. The discovery was followed by the finding of an electron-bifurcating Fd- and NAD-dependent [FeFe]-hydrogenase (HydABC) in Thermotoga maritima (2009), Fd-dependent transhydrogenase (NfnAB) in various bacteria and archaea (2010), Fd- and H2-dependent heterodisulfide reductase (MvhADG-HdrABC) in methanogenic archaea (2011), Fd- and NADH-dependent caffeyl-CoA reductase (CarCDE) in Acetobacterium woodii (2013), Fd- and NAD-dependent formate dehydrogenase (HylABC-FdhF2) in Clostridium acidi-urici (2013), Fd- and NADP-dependent [FeFe]-hydrogenase (HytA-E) in Clostridium autoethanogrenum (2013), Fd(?)- and NADH-dependent methylene-tetrahydrofolate reductase (MetFV-HdrABC-MvhD) in Moorella thermoacetica (2014), Fd- and NAD-dependent lactate dehydrogenase (LctBCD) in A. woodii (2015), Fd- and F420H2-dependent heterodisulfide reductase (HdrA2B2C2) in Methanosarcina acetivorans (2017), and Fd- and NADH-dependent ubiquinol reductase (FixABCX) in Azotobacter vinelandii (2017). The electron-bifurcating flavoprotein complexes known to date fall into four groups that have evolved independently, namely those containing EtfAB (CarED, LctCB, FixBA) with bound FAD, a NuoF homolog (HydB, HytB, or HylB) harboring FMN, NfnB with bound FAD, or HdrA harboring FAD. All these flavoproteins are cytoplasmic except for the membrane-associated protein FixABCX. The organisms—in which they have been found—are strictly anaerobic microorganisms except for the aerobe A. vinelandii. The electron-bifurcating complexes are involved in a variety of processes such as butyric acid fermentation, methanogenesis, acetogenesis, anaerobic lactate oxidation, dissimilatory sulfate reduction, anaerobic- dearomatization, nitrogen fixation, and CO2 fixation. They contribute to energy conservation via the energy-converting ferredoxin: NAD+ reductase complex Rnf or the energy-converting ferredoxin-dependent hydrogenase complex Ech. This Review describes how this mechanism was discovered. PMID:29593673

Technoeconomic Assessment of an Advanced Aqueous Ammonia-Based Postcombustion Capture Process Integrated with a 650-MW Coal-Fired Power Station.

PubMed

Li, Kangkang; Yu, Hai; Yan, Shuiping; Feron, Paul; Wardhaugh, Leigh; Tade, Moses

2016-10-04

Using a rigorous, rate-based model and a validated economic model, we investigated the technoeconomic performance of an aqueous NH 3 -based CO 2 capture process integrated with a 650-MW coal-fired power station. First, the baseline NH 3 process was explored with the process design of simultaneous capture of CO 2 and SO 2 to replace the conventional FGD unit. This reduced capital investment of the power station by US$425/kW (a 13.1% reduction). Integration of this NH 3 baseline process with the power station takes the CO 2 -avoided cost advantage over the MEA process (US$67.3/tonne vs US$86.4/tonne). We then investigated process modifications of a two-stage absorption, rich-split configuration and interheating stripping to further advance the NH 3 process. The modified process reduced energy consumption by 31.7 MW/h (20.2% reduction) and capital costs by US$55.4 million (6.7% reduction). As a result, the CO 2 -avoided cost fell to $53.2/tonne: a savings of $14.1 and $21.9/tonne CO 2 compared with the NH 3 baseline and advanced MEA process, respectively. The analysis of energy breakdown and cost distribution indicates that the technoeconomic performance of the NH 3 process still has great potential to be improved.

Two-electron carbon dioxide reduction catalyzed by rhenium(I) bis(imino)acenaphthene carbonyl complexes.

PubMed

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-05-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile-water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Stability and reactivity of liposome-encapsulated formate dehydrogenase and cofactor system in carbon dioxide gas-liquid flow.

PubMed

Yoshimoto, Makoto; Yamashita, Takayuki; Yamashiro, Takuya

2010-01-01

Formate dehydrogenase from Candida boidinii (CbFDH) is potentially applicable in reduction of CO(2) through oxidation of cofactor NADH into NAD(+). For this, the CbFDH activity needs to be maintained under practical reaction conditions, such as CO(2) gas-liquid flow. In this work, CbFDH and cofactor were encapsulated in liposomes and the liposomal enzymes were characterized in an external loop airlift bubble column. The airlift was operated at 45 degrees C with N(2) or CO(2) as gas phase at the superficial gas velocity U(G) of 2.0 or 3.0 cm/s. The activities of liposomal CbFDH/cofactor systems were highly stable in the airlift regardless of the type of gas phase because liposome membranes prevented interactions of the encapsulated enzyme and cofactor molecules with the gas-liquid interface of bubbles. On the other hand, free CbFDH was deactivated in the airlift especially at high U(G) with CO(2) bubbles. The liposomal CbFDH/NADH could catalyze reduction of CO(2) in the airlift giving the fractional oxidation of the liposomal NADH of 23% at the reaction time of 360 min. The cofactor was kept inside liposomes during the reaction operation with less than 10% of leakage. All of the results obtained demonstrate that the liposomal CbFDH/NADH functions as a stable catalyst for reduction of CO(2) in the airlift. (c) 2010 American Institute of Chemical Engineers

Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems

EPA Science Inventory

Catalytic destruction of benzene (C6H6), a surrogate for organic hazardous air pollutants (HAPs) produced from coal combustion, was investigated using a commercial selective catalytic reduction (SCR) catalyst for evaluating the potential co-benefit of the SCR technology for reduc...

Electrogenerated chemiluminescence. 59. Rhenium complexes

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

Richter, M.M.; Debad, J.D.; Bard, A.J.

Re(L)(CO){sub 3}Cl complexes (where L is 1,10-phenanthroline, 2,2`-bipyridine, or a phenanthroline or bipyridine derivative containing methyl groups) are photoluminescent in fluid solution at room temperature. In acetonitrile solutions, these complexes display one chemically reversible one-electron reduction process and one chemically irreversible oxidation process. {lambda}{sub max} for the luminescence is dependent on the nature of L, and a linear relationship between {lambda}{sub max} and the difference in electrode potentials for oxidation and reduction is evident. Electrogenerated chemiluminescence (ECL) was observed in acetonitrile solutions of these complexes (Bu{sub 4}NPF{sub 6} as electrolyte) by stepping the potential of a Pt disk working electrodemore » between potentials sufficient to form the radical anionic and cationic species. The relative amount of light produced during the anodic and cathodic pulses was dependent on the potential limits and pulse duration. ECL was also generated in the presence of coreactants, i.e., with tri-n-propylamine upon stepping the potential sufficiently positive to form the deprotonated tri-n-propylamine radical and the cationic rhenium(II) species Re{sup II}(L)(CO){sub 3}Cl{sup +}. When S{sub 2}O{sub 8}{sup 2-} was present in solution, ECL was also observed for all of the complexes upon stepping to potentials sufficient to form (Re{sup I}(L)(CO){sub 3}Cl){sup -} and the strong oxidant SO{sub 4}{sup .-}. 44 refs., 8 figs.« less

Rechargeable Al-CO2 Batteries for Reversible Utilization of CO2.

PubMed

Ma, Wenqing; Liu, Xizheng; Li, Chao; Yin, Huiming; Xi, Wei; Liu, Ruirui; He, Guang; Zhao, Xian; Luo, Jun; Ding, Yi

2018-05-21

The excessive emission of CO 2 and the energy crisis are two major issues facing humanity. Thus, the electrochemical reduction of CO 2 and its utilization in metal-CO 2 batteries have attracted wide attention because the batteries can simultaneously accelerate CO 2 fixation/utilization and energy storage/release. Here, rechargeable Al-CO 2 batteries are proposed and realized, which use chemically stable Al as the anode. The batteries display small discharge/charge voltage gaps down to 0.091 V and high energy efficiencies up to 87.7%, indicating an efficient battery performance. Their chemical reaction mechanism to produce the performance is revealed to be 4Al + 9CO 2 ↔ 2Al 2 (CO 3 ) 3 + 3C, by which CO 2 is reversibly utilized. These batteries are envisaged to effectively and safely serve as a potential CO 2 fixation/utilization strategy with stable Al. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water for electricity in India: A multi-model study of future challenges and linkages to climate change mitigation

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

Srinivasan, Shweta; Kholod, Nazar; Chaturvedi, Vaibhav

This paper provides projections of water withdrawals and consumption for electricity generation in India through 2050. Based on the results from five energy-economic modeling teams, the paper explores the implications of economic growth, power plant cooling policies, and electricity CO2 emissions reductions on water withdrawals and consumption. To isolate modeling differences, the five teams used harmonized assumptions regarding economic and population growth, the distribution of power plants by cooling technologies, and withdrawals and consumption intensities. The results demonstrate the different but potentially complementary implications of cooling technology policies and efforts to reduce CO2 emissions. The application of closed-loop cooling technologiesmore » substantially reduces water withdrawals but increases consumption. The water implications of CO2 emissions reductions, depend critically on the approach to these reductions. Focusing on wind and solar power reduces consumption and withdrawals; a focus on nuclear power increases both; and a focus on hydroelectric power could increase consumptive losses through evaporation.« less

The Influence of a CO2 Pricing Scheme on Distributed Energy Resources in California's Commercial Buildings

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

Stadler, Michael; Marnay, Chris; Lai, Judy

2010-06-01

The Ernest Orlando Lawrence Berkeley National Laboratory (LBNL) is working with the California Energy Commission (CEC) to determine the potential role of commercial-sector distributed energy resources (DER) with combined heat and power (CHP) in greenhouse gas emissions (GHG) reductions. Historically, relatively little attention has been paid to the potential of medium-sized commercial buildings with peak electric loads ranging from 100 kW to 5 MW. In our research, we examine how these medium-sized commercial buildings might implement DER and CHP. The buildings are able to adopt and operate various technologies, e.g., photovoltaics (PV), on-site thermal generation, heat exchangers, solar thermal collectors,more » absorption chillers, batteries and thermal storage systems. We apply the Distributed Energy Resources Customer Adoption Model (DER-CAM), which is a mixed-integer linear program (MILP) that minimizes a site?s annual energy costs and/or CO2 emissions. Using 138 representative mid-sized commercial sites in California, existing tariffs of major utilities, and expected performance data of available technologies in 2020, we find the GHG reduction potential for these buildings. We compare different policy instruments, e.g., a CO2 pricing scheme or a feed-in tariff (FiT), and show their contributions to the California Air Resources Board (CARB) goals of additional 4 GW CHP capacities and 6.7 Mt/a GHG reduction in California by 2020. By applying different price levels for CO2, we find that there is competition between fuel cells and PV/solar thermal. It is found that the PV/solar thermal adoption increases rapidly, but shows a saturation at high CO2 prices, partly due to limited space for PV and solar thermal. Additionally, we find that large office buildings are good hosts for CHP in general. However, most interesting is the fact that fossil-based CHP adoption also increases with increasing CO2 prices. We will show service territory specific results since the attractiveness of DER varies widely by climate zone and service territory.« less

Design of a catalyst through Fe doping of the boron cage B10H14 for CO2 hydrogenation and investigation of the catalytic character of iron hydride (Fe-H).

PubMed

Qian, Lei; Ma, Kai-Yang; Zhou, Zhong-Jun; Ma, Fang

2017-12-13

The innovative catalyst Fe@B 10 H 14 is designed through Fe doping of the boron cage B 10 H 14 and is employed to catalyze CO 2 hydrogenation using a quantum mechanical method. First, the structure of the Fe@B 10 H 14 complex is characterized through calculated 11 B NMR chemical shifts and Raman spectra, and the interactions between Fe and the four H atoms of the opening in the cage are analyzed, which show that various iron hydride (Fe-H) characteristics exist. Subsequently, the potential of Fe@B 10 H 14 as a catalyst for the hydrogenative reduction of CO 2 in the gas phase is computationally evaluated. We find that an equivalent of Fe@B 10 H 14 can consecutively reduce double CO 2 to obtain the double product HCOOH through a two-step reduction, and Fe@B 10 H 12 and Fe@B 10 H 10 are successively obtained. The Fe presents single-atom character in the reduction of CO 2 , which is different from the common iron(ii) catalyzed CO 2 reduction. The calculated total free energy barrier of the first CO 2 reduction is only 8.79 kcal mol -1 , and that of the second CO 2 reduction is 25.71 kcal mol -1 . Every reduction reaction undergoes two key transition states TSC-H and TSO-H. Moreover, the transition state of the C-H bond formation TSC-H is the rate-determining step, where the interaction between π C[double bond, length as m-dash]O * and the weak σ Fe-H bond plays an important role. Furthermore, the hydrogenations of Fe@B 10 H 12 and Fe@B 10 H 10 are investigated, which aim at determining the ability of Fe-H circulation in the Fe doped decaborane complex. We find that the hydrogenation of Fe@B 10 H 10 undergoes a one-step H 2 -adsorbed transition state TSH-adsorb with an energy barrier of 6.42 kcal mol -1 from Fe@B 10 H 12 . Comparing with the hydrogenation of Fe@B 10 H 10 , it is slightly more difficult for the hydrogenation of Fe@B 10 H 12 , where the rate-determining step is the H 2 -cleaved transition state TS2H-H with an energy barrier of 17.38 kcal mol -1 .

A view of aqueous electrochemical carbon dioxide reduction to formate at indium electrodes, and the reversible electrodeposition of silver in ionic liquids through the lens of fundamental surface science

NASA Astrophysics Data System (ADS)

Detweiler, Zachary M.

Two systems were studied using in situ measurement techniques, demonstrating the importance of creative experimental design. The electroreduction of CO2 at heterogeneous indium electrodes in aqueous solution was analyzed by cyclic voltammetry. Bulk electrolyses showed that increased indium oxide presence prior to electrolysis improved the Faradaic efficiency of CO 2 reduction to formate in 0.5 M K2SO2 aqueous solutions at a pH of 4.4. In order to more accurately assign speciation at the electrode surface ex situ O2 and H2O dosing of metallic indium under UHV was studied with XPS, HREELS and TPD. Ambient pressure XPS showed that the ratio of oxide to hydroxide at the indium interface is strongly dependent on the partial pressure of water; decreasing as P(H2O) increases. Using this information, a qualitative picture of the indium interface could be generated. In situ ATR-FTIR with an indium thin film as the working electrode showed that bulk oxide quickly reduces with applied potential, but an interfacial oxide is still present at high reductive overpotential. Additionally, an adsorbed carbonate at the thin film interface was observed upon introducing CO 2 to the cell. The implication of a surface bound carbonate as the CO 2 reduction intermediate draws on a mechanism that has not previously been discussed in the electrochemical reduction of CO2. The previous study of this mechanism from Ficscher-Tropsch literature helps to predict the further reduced products found at more electropositive metals, such as copper or magnesium, the latter of which is described here. Additionaly described here is a series of ILs that were employed as electrolyte for reversible silver deposition. BMIM N(TfO)2 was found to be the most promising of those studied, intrinsically giving a more uniform deposit that was bright and reversible. Deposit formation was studied using SEM and EDX as a function of deposition potential and deposition time. In situ reflectometry was employed to get a direct measure of deposit reflectivity on ITO coated glass as a function of time. A promising device system has been elucidated as a result and future considerations have been identified from coincident electrochemical and spectroscopic measurements.

Achieving CO 2 reductions in Colombia: Effects of carbon taxes and abatement targets

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

Calderón, Silvia; Alvarez, Andres Camilo; Loboguerrero, Ana Maria

In this paper we investigate CO 2 emission scenarios for Colombia and the effects of implementing carbon taxes and abatement targets on the energy system. By comparing baseline and policy scenario results from two integrated assessment partial equilibrium models TIAM-ECN and GCAM and two general equilibrium models Phoenix and MEG4C, we provide an indication of future developments and dynamics in the Colombian energy system. Currently, the carbon intensity of the energy system in Colombia is low compared to other countries in Latin America. However, this trend may change given the projected rapid growth of the economy and the potential increasemore » in the use of carbon-based technologies. Climate policy in Colombia is under development and has yet to consider economic instruments such as taxes and abatement targets. This paper shows how taxes or abatement targets can achieve significant CO 2 reductions in Colombia. Though abatement may be achieved through different pathways, taxes and targets promote the entry of cleaner energy sources into the market and reduce final energy demand through energy efficiency improvements and other demand-side responses. The electric power sector plays an important role in achieving CO 2 emission reductions in Colombia, through the increase of hydropower, the introduction of wind technologies, and the deployment of biomass, coal and natural gas with CO 2 capture and storage (CCS). Uncertainty over the prevailing mitigation pathway reinforces the importance of climate policy to guide sectors toward low-carbon technologies. This paper also assesses the economy-wide implications of mitigation policies such as potential losses in GDP and consumption. As a result, an assessment of the legal, institutional, social and environmental barriers to economy-wide mitigation policies is critical yet beyond the scope of this paper.« less

Life cycle assessment of biochar systems: estimating the energetic, economic, and climate change potential.

PubMed

Roberts, Kelli G; Gloy, Brent A; Joseph, Stephen; Scott, Norman R; Lehmann, Johannes

2010-01-15

Biomass pyrolysis with biochar returned to soil is a possible strategy for climate change mitigation and reducing fossil fuel consumption. Pyrolysis with biochar applied to soils results in four coproducts: long-term carbon (C) sequestration from stable C in the biochar, renewable energy generation, biochar as a soil amendment, and biomass waste management. Life cycle assessment was used to estimate the energy and climate change impacts and the economics of biochar systems. The feedstocks analyzed represent agricultural residues (corn stover), yard waste, and switchgrass energy crops. The net energy of the system is greatest with switchgrass (4899 MJ t(-1) dry feedstock). The net greenhouse gas (GHG) emissions for both stover and yard waste are negative, at -864 and -885 kg CO(2) equivalent (CO(2)e) emissions reductions per tonne dry feedstock, respectively. Of these total reductions, 62-66% are realized from C sequestration in the biochar. The switchgrass biochar-pyrolysis system can be a net GHG emitter (+36 kg CO(2)e t(-1) dry feedstock), depending on the accounting method for indirect land-use change impacts. The economic viability of the pyrolysis-biochar system is largely dependent on the costs of feedstock production, pyrolysis, and the value of C offsets. Biomass sources that have a need for waste management such as yard waste have the highest potential for economic profitability (+$69 t(-1) dry feedstock when CO(2)e emission reductions are valued at $80 t(-1) CO(2)e). The transportation distance for feedstock creates a significant hurdle to the economic profitability of biochar-pyrolysis systems. Biochar may at present only deliver climate change mitigation benefits and be financially viable as a distributed system using waste biomass.

Achieving CO 2 reductions in Colombia: Effects of carbon taxes and abatement targets

DOE PAGES

Calderón, Silvia; Alvarez, Andres Camilo; Loboguerrero, Ana Maria; ...

2015-06-03

In this paper we investigate CO 2 emission scenarios for Colombia and the effects of implementing carbon taxes and abatement targets on the energy system. By comparing baseline and policy scenario results from two integrated assessment partial equilibrium models TIAM-ECN and GCAM and two general equilibrium models Phoenix and MEG4C, we provide an indication of future developments and dynamics in the Colombian energy system. Currently, the carbon intensity of the energy system in Colombia is low compared to other countries in Latin America. However, this trend may change given the projected rapid growth of the economy and the potential increasemore » in the use of carbon-based technologies. Climate policy in Colombia is under development and has yet to consider economic instruments such as taxes and abatement targets. This paper shows how taxes or abatement targets can achieve significant CO 2 reductions in Colombia. Though abatement may be achieved through different pathways, taxes and targets promote the entry of cleaner energy sources into the market and reduce final energy demand through energy efficiency improvements and other demand-side responses. The electric power sector plays an important role in achieving CO 2 emission reductions in Colombia, through the increase of hydropower, the introduction of wind technologies, and the deployment of biomass, coal and natural gas with CO 2 capture and storage (CCS). Uncertainty over the prevailing mitigation pathway reinforces the importance of climate policy to guide sectors toward low-carbon technologies. This paper also assesses the economy-wide implications of mitigation policies such as potential losses in GDP and consumption. As a result, an assessment of the legal, institutional, social and environmental barriers to economy-wide mitigation policies is critical yet beyond the scope of this paper.« less

Physiological effects on fishes in a high-CO2 world

NASA Astrophysics Data System (ADS)

Ishimatsu, Atsushi; Hayashi, Masahiro; Lee, Kyoung-Seon; Kikkawa, Takashi; Kita, Jun

2005-09-01

Fish are important members of both freshwater and marine ecosystems and constitute a major protein source in many countries. Thus potential reduction of fish resources by high-CO2 conditions due to the diffusion of atmospheric CO2 into the surface waters or direct CO2 injection into the deep sea can be considered as another potential threat to the future world population. Fish, and other water-breathing animals, are more susceptible to a rise in environmental CO2 than terrestrial animals because the difference in CO2 partial pressure (PCO2) of the body fluid of water-breathing animals and ambient medium is much smaller (only a few torr (1 torr = 0.1333 kPa = 1316 μatm)) than in terrestrial animals (typically 30-40 torr). A survey of the literature revealed that hypercapnia acutely affects vital physiological functions such as respiration, circulation, and metabolism, and changes in these functions are likely to reduce growth rate and population size through reproduction failure and change the distribution pattern due to avoidance of high-CO2 waters or reduced swimming activities. This paper reviews the acute and chronic effects of CO2 on fish physiology and tries to clarify necessary areas of future research.

Effect of supercritical carbon dioxide pasteurization on natural microbiota, texture, and microstructure of fresh-cut coconut.

PubMed

Ferrentino, Giovanna; Balzan, Sara; Dorigato, Andrea; Pegoretti, Alessandro; Spilimbergo, Sara

2012-05-01

The objective of the present study was the evaluation of the effectiveness of supercritical carbon dioxide (SC-CO(2)) as a nonthermal technology for the pasteurization of fresh-cut coconut, as an example of ready-to-eat and minimally processed food. First, the inactivation kinetics of microbiota on coconut were determined using SC-CO(2) treatments (pressures at 8 and 12 MPa, temperatures from 24 to 45 °C, treatment times from 5 to 60 min). Second, the effects of SC-CO(2) on the hardness and microstructure of fresh-cut coconut processed at the optimal conditions for microbial reduction were investigated. SC-CO(2) treatment of 15 min at 45 °C and 12 MPa induced 4 log CFU/g reductions of mesophilic microorganisms, lactic acid bacteria, total coliforms, and yeasts and molds. The hardness of coconut was not affected by the treatment but the samples developed an irregular and disorderly microstructure. Results suggested the potential of SC-CO(2) in preserving fresh-cut fruits and ready-to-eat products. © 2012 Institute of Food Technologists®

Membraneless laminar flow cell for electrocatalytic CO 2 reduction with liquid product separation

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

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei

The production of liquid fuel products via electrochemical reduction of CO 2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O 2) from reaching the cathode. Ion-conducting membranes have been applied in CO 2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flowmore » cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO 2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.« less

Membraneless laminar flow cell for electrocatalytic CO 2 reduction with liquid product separation

DOE PAGES

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei; ...

2017-03-16

The production of liquid fuel products via electrochemical reduction of CO 2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O 2) from reaching the cathode. Ion-conducting membranes have been applied in CO 2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flowmore » cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO 2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.« less

Urban cross-sector actions for carbon mitigation with local health co-benefits in China

NASA Astrophysics Data System (ADS)

Ramaswami, Anu; Tong, Kangkang; Fang, Andrew; Lal, Raj M.; Nagpure, Ajay Singh; Li, Yang; Yu, Huajun; Jiang, Daqian; Russell, Armistead G.; Shi, Lei; Chertow, Marian; Wang, Yangjun; Wang, Shuxiao

2017-10-01

Cities offer unique strategies to reduce fossil fuel use through the exchange of energy and materials across homes, businesses, infrastructure and industries co-located in urban areas. However, the large-scale impact of such strategies has not been quantified. Using new models and data sets representing 637 Chinese cities, we find that such cross-sectoral strategies--enabled by compact urban design and circular economy policies--contribute an additional 15%-36% to national CO2 mitigation, compared to conventional single-sector strategies. As a co-benefit, ~25,500 to ~57,500 deaths annually are avoided from air pollution reduction. The benefits are highly variable across cities, ranging from <1%-37% for CO2 emission reduction and <1%-47% for avoided premature deaths. These results, using multi-scale, multi-sector physical systems modelling, identify cities with high carbon and health co-benefit potential and show that urban-industrial symbiosis is a significant carbon mitigation strategy, achievable with a combination of existing and advanced technologies in diverse city types.

A wedge-based approach to estimating health co-benefits of climate change mitigation activities in the United States

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

Balbus, John M.; Greenblatt, Jeffery B.; Chari, Ramya

While it has been recognized that actions reducing greenhouse gas (GHG) emissions can have significant positive and negative impacts on human health through reductions in ambient fine particulate matter (PM2.5) concentrations, these impacts are rarely taken into account when analyzing specific policies. This study presents a new framework for estimating the change in health outcomes resulting from implementation of specific carbon dioxide (CO 2) reduction activities, allowing comparison of different sectors and options for climate mitigation activities. Our estimates suggest that in the year 2020, the reductions in adverse health outcomes from lessened exposure to PM2.5 would yield economic benefitsmore » in the range of $6 to $14 billion (in 2008 USD), depending on the specific activity. This equates to between $40 and $93 per metric ton of CO 2 in health benefits. Specific climate interventions will vary in the health co-benefits they provide as well as in potential harms that may result from their implementation. Rigorous assessment of these health impacts is essential for guiding policy decisions as efforts to reduce GHG emissions increase in scope and intensity.« less

Climate impacts of air quality policy: switching to a natural gas-fueled public transportation system in New Delhi.

PubMed

Reynolds, Conor C O; Kandlikar, Milind

2008-08-15

Between 2001 and 2003, public transport vehicles in New Delhi were required to switch their fuel to natural gas in an attemptto reduce their air pollution impacts. This study examines the climatic impacts of New Delhi's fuel switching policy, and outlines implications for such efforts in rapidly industrializing countries. Natural gas is mostly composed of methane, an important greenhouse gas. Emitted aerosols (black carbon, particulate organic carbon, and sulfate) also cause radiative forcing. We find that methane and black carbon emissions are critical contributors to the change in carbon dioxide equivalent [CO2(e)] emissions. In New Delhi, the switch to natural gas results in a 30% increase in CO2(e) when the impact of aerosols is not considered. However, when aerosol emissions are taken into account in our model, the net effect of the switch is estimated to be a 10% reduction in CO2(e), and there may be as much as a 30% reduction in CO2(e). There is significant potential for emissions reductions through the United Nations Framework Convention on Climate Change (UNFCCC) Clean Development Mechanism for such fuel switching projects.

Photocatalytic CO 2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO 2, CO, or Proton

DOE PAGES

Shimoda, Tomoe; Morishima, Takeshi; Kodama, Koichi; ...

2018-04-26

Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO 2) reduction with Ru(bpy) 3 2+ as a photosensitizer, tri-p-tolylamine (TTA) as a reversible quencher, and triethylamine (TEA) as a sacrificial electron donor to produce carbon monoxide and dihydrogen. Here, the CO 2 reduction is slow because of the large structural changes, spin flipping in the cobalt catalytic intermediates, and an uphill reaction for reduction to catalytically active Co(0) by the photoproduced [Ru(bpy) 3] +.

Photocatalytic CO 2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO 2, CO, or Proton

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

Shimoda, Tomoe; Morishima, Takeshi; Kodama, Koichi

Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO 2) reduction with Ru(bpy) 3 2+ as a photosensitizer, tri-p-tolylamine (TTA) as a reversible quencher, and triethylamine (TEA) as a sacrificial electron donor to produce carbon monoxide and dihydrogen. Here, the CO 2 reduction is slow because of the large structural changes, spin flipping in the cobalt catalytic intermediates, and an uphill reaction for reduction to catalytically active Co(0) by the photoproduced [Ru(bpy) 3] +.

Plasma for electrification of chemical industry: a case study on CO2 reduction

NASA Astrophysics Data System (ADS)

van Rooij, G. J.; Akse, H. N.; Bongers, W. A.; van de Sanden, M. C. M.

2018-01-01

Significant growth of the share of (intermittent) renewable power in the chemical industry is imperative to meet increasingly stricter limits on CO2 exhaust that are being implemented within Europe. This paper aims to evaluate the potential of a plasma process that converts input CO2 into a pure stream of CO to aid in renewable energy penetration in this sector. A realistic process design is constructed to serve as a basis for an economical analysis. The manufacturing cost price of CO is estimated at 1.2 kUS ton-1 CO. A sensitivity analysis shows that separation is the dominant cost factor, so that improving conversion is currently more effective to lower the price than e.g. energy efficiency.

The steps of activating a prospective CO 2 hydrogenation catalyst with combined CO 2 capture and reduction

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

Lao, D. B.; Galan, B. R.; Linehan, J. C.

2016-08-10

Combining carbon capture and reduction is an efficient strategy to alleviate the high energy requirements for seperation, compression, and storage of CO2 prior to reduction. Recent studies have shown that catalytic hydrogenations of CO2 can be performed without added pressure of CO2 using switchable ionic liquids. It’s ambiguous whether the alkylcarbonate (captured CO2) is reduced as it is in dynamic equilibrium with neutral CO2 in solution. New studies are presented to elucidate the reactivity of CO2 and CO2 captured in solution.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

Cu2O-tipped ZnO nanorods with enhanced photoelectrochemical performance for CO2 photoreduction

NASA Astrophysics Data System (ADS)

Iqbal, Muzaffar; Wang, Yanjie; Hu, Haifeng; He, Meng; Hassan Shah, Aamir; Lin, Lin; Li, Pan; Shao, Kunjuan; Reda Woldu, Abebe; He, Tao

2018-06-01

The design of Cu2O-tipped ZnO nanorods is proposed here aiming at enhanced photoelectrochemical properties. The tip-selective deposition of Cu2O is confirmed by scanning transmission electron microscopy (STEM). The photoinduced charge behavior like charge generation, separation and transport has been thoroughly studied by UV-vis absorption analysis and different photoelectrochemical characterizations, including transient photocurrent, incident photon-to-current efficiency (IPCE), electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS), and Mott-Schottky measurements. The photoelectrochemical characterizations clearly indicate that ZnO/Cu2O structures exhibit much higher performance than pristine ZnO, due to the formation of p-n junction, as well as the tip selective growth of Cu2O on ZnO. Photocatalytic CO2 reduction in aqueous solution under UV-visible light illumination shows that CO is the main product, and with the increase of the Cu2O content in the heterostructure, the CO yield increases. This work shows that Cu2O-tipped ZnO nanorods possess improved behavior of charge generation, separation and transport, which may work as a potential candidate for photocatalytic CO2 reduction.

Evaluation of homogeneous electrocatalysts by cyclic voltammetry.

PubMed

Rountree, Eric S; McCarthy, Brian D; Eisenhart, Thomas T; Dempsey, Jillian L

2014-10-06

The pursuit of solar fuels has motivated extensive research on molecular electrocatalysts capable of evolving hydrogen from protic solutions, reducing CO2, and oxidizing water. Determining accurate figures of merit for these catalysts requires the careful and appropriate application of electroanalytical techniques. This Viewpoint first briefly presents the fundamentals of cyclic voltammetry and highlights practical experimental considerations before focusing on the application of cyclic voltammetry for the characterization of electrocatalysts. Key metrics for comparing catalysts, including the overpotential (η), potential for catalysis (E(cat)), observed rate constant (k(obs)), and potential-dependent turnover frequency, are discussed. The cyclic voltammetric responses for a general electrocatalytic one-electron reduction of a substrate are presented along with methods to extract figures of merit from these data. The extension of this analysis to more complex electrocatalytic schemes, such as those responsible for H2 evolution and CO2 reduction, is then discussed.

A Model of Carbon Capture and Storage with Demonstration of Global Warming Potential and Fossil Fuel Resource Use Efficiency

NASA Astrophysics Data System (ADS)

Suebsiri, Jitsopa

Increasing greenhouse gas concentration in the atmosphere influences global climate change even though the level of impact is still unclear. Carbon dioxide capture and storage (CCS) is increasingly seen as an important component of broadly based greenhouse gas reduction measures. Although the other greenhouse gases are more potent, the sheer volume of CO 2 makes it dominant in term of its effect in the atmosphere. To understand the implications, CCS activities should be studied from a full life cycle perspective. This thesis outlines the successful achievement of the objectives of this study in conducting life cycle assessment (LCA), reviewing the carbon dioxide implications only, combining two energy systems, coal-fired electrical generations and CO2 used for enhanced oil recovery (EOR). LCA is the primary approach used in this study to create a tool for CCS environmental evaluation. The Boundary Dam Power Station (BDPS) and the Weyburn-Midale CO 2 EOR Project in Saskatchewan, Canada, are studied and adopted as case scenarios to find the potential for effective application of CCS in both energy systems. This study demonstrates two levels of retrofitting of the BDPS, retrofit of unit 3 or retrofit of all units, combined with three options for CO 2 geological storage: deep saline aquifer, CO2 EOR, and a combination of deep saline aquifer storage and CO2 EOR. Energy output is considered the product of combining these two energy resources (coal and oil). Gigajoules (GJ) are used as the fundamental unit of measurement in comparing the combined energy types. The application of this tool effectively demonstrates the results of application of a CCS system concerning global warming potential (GWP) and fossil fuel resource use efficiency. Other environmental impacts could be analyzed with this tool as well. In addition, the results demonstrate that the GWP reduction is directly related to resource use efficiency. This means the lower the GWP of CCS, the lower resource use efficiency as well. Three processes, coal mining, power production including CO2 capture unit operation, and crude oil usage, must be included when the GWP of CCS is calculated. Moreover, the results from the sensitivity analysis of power generation efficiency present not only a significant reduction of GWP, but also a competitive solution for improving or at least preventing the decrease of fossil fuel resource use efficiency when CCS is applied.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+Soultion : Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Dai, C.; Zhang, Y.

2015-12-01

The nanoscale particle and low oxidation reduction potential make nano zero-valent iron (nZVI) an efficient sorbent and reductant for treating many kinds of organic contaminants and heavy metals.The structures of nanoscale zero-valent iron (nZVI) particles are evolving in reactions, and the reactions are influenced by the evolved structures. In order to understand the detail removal process, it is important to investigate the interactions between reactions and structural evolution. In this work, reactions between nZVI and Co2+ at different initial concentrations in anoxic aqueous solutions (to eliminate the effects of O2) were tracked for 10 days using a variety of methods including inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution-transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). Continuous removal and reduction of Co2+ by nZVI caused by structural evolution were revealed in reaction processes. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the corrosion rate of nZVI, was deemed as the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results showed that the formation and dissolution of sheet structure impacts on the ratio of Fe (0) on nZVI's surface and the surface reduction of Co2+. The cavity structure provides the possibility of Co migrating from surface to inside of nZVI leading a continuous removal. A subacidity condition could accelerate the evolution to improve the removal of Co2+ and the results of structural controlled reactions further indicated that the removal was suspended by sheet structure and enhanced by cavity structure. The results in this study revealed "structural influence" for fully and dynamically understanding nZVI's reactions.

Organic reductants based leaching: A sustainable process for the recovery of valuable metals from spent lithium ion batteries.

PubMed

Chen, Xiangping; Guo, Chunxiu; Ma, Hongrui; Li, Jiazhu; Zhou, Tao; Cao, Ling; Kang, Duozhi

2018-05-01

It is significant to recover metal values from spent lithium ion batteries (LIBs) for the alleviation or prevention of potential risks towards environmental pollution and public health, as well as for the conservation of valuable metals. Herein a hydrometallurgical process was proposed to explore the possibility for the leaching of different metals from waste cathodic materials (LiCoO 2 ) of spent LIBs using organics as reductant in sulfuric acid medium. According to the leaching results, about 98% Co and 96% Li can be leached under the optimal experimental conditions of reaction temperature - 95 °C, reaction time - 120 min, reductive agent dosage - 0.4 g/g, slurry density - 25 g/L, concentration of sulfuric acid-3 mol/L in H 2 SO 4  + glucose leaching system. Similar results (96% Co and 100% Li) can be obtained in H 2 SO 4  + sucrose leaching system under optimized leaching conditions. Despite a complete leaching of Li (∼100%), only 54% Co can be dissolved in the H 2 SO 4  + cellulose leaching system under optimized leaching conditions. Finally, different characterization methods, including UV-Vis, FT-IR, SEM and XRD, were employed for the tentative exploration of reductive leaching reactions using organic as reductant in sulfuric acid medium. All the leaching and characterization results confirm that both glucose and sucrose are effective reductants during leaching, while cellulose should be further degraded to organics with low molecular weights to achieve a satisfactory leaching performance. Copyright © 2018 Elsevier Ltd. All rights reserved.

The role of ecosystem-atmosphere interactions in simulated Amazonian precipitation decrease and forest dieback under global climate warming

NASA Astrophysics Data System (ADS)

Betts, R. A.; Cox, P. M.; Collins, M.; Harris, P. P.; Huntingford, C.; Jones, C. D.

A suite of simulations with the HadCM3LC coupled climate-carbon cycle model is used to examine the various forcings and feedbacks involved in the simulated precipitation decrease and forest dieback. Rising atmospheric CO2 is found to contribute 20% to the precipitation reduction through the physiological forcing of stomatal closure, with 80% of the reduction being seen when stomatal closure was excluded and only radiative forcing by CO2 was included. The forest dieback exerts two positive feedbacks on the precipitation reduction; a biogeophysical feedback through reduced forest cover suppressing local evaporative water recycling, and a biogeochemical feedback through the release of CO2 contributing to an accelerated global warming. The precipitation reduction is enhanced by 20% by the biogeophysical feedback, and 5% by the carbon cycle feedback from the forest dieback. This analysis helps to explain why the Amazonian precipitation reduction simulated by HadCM3LC is more extreme than that simulated in other GCMs; in the fully-coupled, climate-carbon cycle simulation, approximately half of the precipitation reduction in Amazonia is attributable to a combination of physiological forcing and biogeophysical and global carbon cycle feedbacks, which are generally not included in other GCM simulations of future climate change. The analysis also demonstrates the potential contribution of regional-scale climate and ecosystem change to uncertainties in global CO2 and climate change projections. Moreover, the importance of feedbacks suggests that a human-induced increase in forest vulnerability to climate change may have implications for regional and global scale climate sensitivity.

The effect of elevated [CO{sub 2}] on growth and photosynthesis of two eucalyptus species exposed to high temperatures and water deficits

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

Roden, J.S.; Ball, M.C.

1996-07-01

Two species of eucalyptus (Eucalyptus macrorhyncha and Eucalyptus rossii) were grown for 8 weeks in either ambient (350 {mu}L L{sup {minus}1}) or elevated (700 {mu}L L{sup {minus}1}) CO{sub 2} concentrations, either well watered or without water additions, and subjected to a daily, 3-h high-temperature (45{degrees}C, maximum) and high-light (1250 {mu}mol photons m{sup {minus}2} s{sup {minus}1}, maximum) stress period. Water-stressed seedlings of E. macrorhyncha had higher leaf water potentials when grown in elevated [CO{sub 2}]. Growth analysis indicated that increased [CO{sub 2}] may allow eucalyptus species to perform better during conditions of low soil moisture. A down-regulation of photosynthetic capacity wasmore » observed for seedlings grown in elevated [CO{sub 2}] when well watered but not when water stressed. Well-water seedlings grown in elevated [CO{sub 2}] had lower quantum efficiencies as measured by chlorophyll fluorescence (the ratio of variable to maximal chlorophyll fluorescence [F{sub v}/F{sub m}]) than seedlings grown in ambine [CO{sub 2}] during the high-temperature stress period. However, no significant differences in F{sub v}/F{sub m} were observed between CO{sub 2} treatments when water was withheld. The reductions in dark-adapted F{sub v}/F{sub m} for plants grown in elevated [CO{sub 2}] were not well correlated with increased xanthophyll cycle photoprotection. However, reductions in the F{sub v}/F{sub m} were correlated with increased levels of nonstructural carbohydrates. The reduction in quantum efficiencies for plants grown in elevated [CO{sub 2}] is discussed in the context of feedback inhibition of electron transport associated with starch accumulation and variation in sink strength. 48 refs., 8 figs., 2 figs.« less

Chloroethene Biodegradation Potential, ADOT/PF Peger Road Maintenance Facility, Fairbanks, Alaska

USGS Publications Warehouse

Bradley, Paul M.; Chapelle, Frances H.

2004-01-01

A series of 14C-radiotracer-based microcosm experiments were conducted to assess: 1) the extent, rate and products of microbial dechlorination of trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinyl chloride (VC) in sediments at the Peger Road site; 2) the effect of three electron donor amendments (molasses, shrimp and crab chitin, and 'Hydrogen Release Compound' (HRC)) on microbial degradation of TCE in three Peger Road sediments; and 3) the potential significance at the site of chloroethene biodegradation processes other than reductive dechlorination. In these experiments, TCE biodegradation yielded the reduced products, DCE and VC, and the oxidation product CO 2. Biodegradation of DCE and VC involved stoichiometric oxidation to CO 2. Both laboratory microcosm study and field redox assessment results indicated that the predominant terminal electron accepting process in Peger Road plume sediments under anoxic conditions was Mn/Fe-reduction. The rates of chloroethene biodegradation observed in Peger Road sediment microcosms under low temperature conditions (4?C) were within the range of those observed in sediments from temperate (20?C) aquifer systems. This result confirmed that biodegradation can be a significant mechanism for in situ contaminant remediation even in cold temperature aquifers. The fact that CO2 was the sole product of cis-DCE and VC biodegradation detected in Peger Road sediments indicated that a natural attenuation assessment based on reduced daughter product accumulation may significantly underestimate the potential for DCE and VC biodegradation at the Peger Road. Neither HRC nor molasses addition stimulated TCE reductive dechlorination. The fact that molasses and HRC amendment did stimulate Mn/Fe-reduction suggests that addition of these electron donors favored microbial Mn/Fe-reduction to the detriment of microbial TCE dechlorinating activity. In contrast, amendment of sediment microcosms with shrimp and crab chitin resulted in the establishment of mixed Mn/Fe-reducing, SO42--reducing and methanogenic conditions and enhanced TCE biodegradation in two of three Peger Road sediment treatments.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid.

PubMed

Asadi, Mohammad; Kim, Kibum; Liu, Cong; Addepalli, Aditya Venkata; Abbasi, Pedram; Yasaei, Poya; Phillips, Patrick; Behranginia, Amirhossein; Cerrato, José M; Haasch, Richard; Zapol, Peter; Kumar, Bijandra; Klie, Robert F; Abiade, Jeremiah; Curtiss, Larry A; Salehi-Khojin, Amin

2016-07-29

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform that concurrently oxidized water in the absence of any external potential. Copyright © 2016, American Association for the Advancement of Science.

Net radiative forcing responses to regional CO and NMVOC reductions

NASA Astrophysics Data System (ADS)

Fry, M. M.; Schwarzkopf, M. D.; Adelman, Z.; Naik, V.; West, J.

2012-12-01

Recent studies suggest that short-lived pollutants and their precursors be considered in near-term climate mitigation strategies, in addition to national air quality programs, but their associated forcings vary based on the region of emissions. Here we quantify the net radiative forcing (RF) impacts of regional anthropogenic carbon monoxide (CO) and non-methane volatile organic compound (NMVOC) emissions due to changes in the tropospheric concentrations of ozone (O3), methane (CH4), and aerosols (carbonaceous and sulfate), to inform future coordinated actions addressing air quality and climate forcing. We present the RF from CO and NMVOC emission reductions from 10 regions (North America, South America, Europe, Former Soviet Union, Southern Africa, India, East Asia, Southeast Asia, Australia and New Zealand, and Middle East and Northern Africa). The global chemical transport model MOZART-4 is used to simulate tropospheric concentration changes, using the IPCC AR5 Representative Concentration Pathway 8.5 (RCP 8.5) emissions inventory for 2005 and global meteorology from the Goddard Earth Observing System Model, version 5 (GEOS-5) for the years 2004-2005. We utilize the NOAA Geophysical Fluid Dynamics Laboratory standalone radiative transfer model to calculate the stratospheric-adjusted net RF for each regional CO and NMVOC reduction, relative to the base. We find that global annual net RF per unit change in emissions ranges from -0.115 to -0.131 mW m-2 / Tg CO for CO reductions, and -0.0035 to -0.436 mW m-2 / Tg C for NMVOC reductions, with the regions in the tropics providing the greatest improvements (Middle East, Southeast Asia, and India CO reductions, and Middle East, Africa, and India NMVOC reductions). The net RF distributions for the CO and NMVOC reductions show widespread cooling across the northern and southern hemispheres corresponding to the patterns of O3 and CH4 decreases, and localized positive and negative net RFs due to increases and decreases in aerosols. The strongest annual net RF impacts occur within the tropics (28 S - 28 N) followed by the northern mid-latitudes (28 N - 60 N), independent of reduction region for CO, and for many of the NMVOC regional reductions. The small variation in RF per unit emissions for CO, among world regions (coefficient of variation = 0.045), suggests that the error would be small in using a uniform global warming potential (GWP), and in possibly including CO in international climate agreements. In contrast, NMVOCs show greater variability among the reduction regions (coefficient of variation = 0.48), suggesting that regionally-specific GWPs may be more appropriate for NMVOCs.

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.

Fabricating Ir/C Nanofiber Networks as Free-Standing Air Cathodes for Rechargeable Li-CO2 Batteries.

PubMed

Wang, Chengyi; Zhang, Qinming; Zhang, Xin; Wang, Xin-Gai; Xie, Zhaojun; Zhou, Zhen

2018-06-07

Li-CO 2 batteries are promising energy storage systems by utilizing CO 2 at the same time, though there are still some critical barriers before its practical applications such as high charging overpotential and poor cycling stability. In this work, iridium/carbon nanofibers (Ir/CNFs) are prepared via electrospinning and subsequent heat treatment, and are used as cathode catalysts for rechargeable Li-CO 2 batteries. Benefitting from the unique porous network structure and the high activity of ultrasmall Ir nanoparticles, Ir/CNFs exhibit excellent CO 2 reduction and evolution activities. The Li-CO 2 batteries present extremely large discharge capacity, high coulombic efficiency, and long cycling life. Moreover, free-standing Ir/CNF films are used directly as air cathodes to assemble Li-CO 2 batteries, which show high energy density and ultralong operation time, demonstrating great potential for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inorganic Nanoparticles/Metal Organic Framework Hybrid Membrane Reactors for Efficient Photocatalytic Conversion of CO2.

PubMed

Maina, James W; Schütz, Jürg A; Grundy, Luke; Des Ligneris, Elise; Yi, Zhifeng; Kong, Lingxue; Pozo-Gonzalo, Cristina; Ionescu, Mihail; Dumée, Ludovic F

2017-10-11

Photocatalytic conversion of carbon dioxide (CO 2 ) to useful products has potential to address the adverse environmental impact of global warming. However, most photocatalysts used to date exhibit limited catalytic performance, due to poor CO 2 adsorption capacity, inability to efficiently generate photoexcited electrons, and/or poor transfer of the photogenerated electrons to CO 2 molecules adsorbed on the catalyst surface. The integration of inorganic semiconductor nanoparticles across metal organic framework (MOF) materials has potential to yield new hybrid materials, combining the high CO 2 adsorption capacity of MOF and the ability of the semiconductor nanoparticles to generate photoexcited electrons. Herein, controlled encapsulation of TiO 2 and Cu-TiO 2 nanoparticles within zeolitic imidazolate framework (ZIF-8) membranes was successfully accomplished, using rapid thermal deposition (RTD), and their photocatalytic efficiency toward CO 2 conversion was investigated under UV irradiation. Methanol and carbon monoxide (CO) were found to be the only products of the CO 2 reduction, with yields strongly dependent upon the content and composition of the dopant semiconductor particles. CuTiO 2 nanoparticle doped membranes exhibited the best photocatalytic performance, with 7 μg of the semiconductor nanoparticle enhancing CO yield of the pristine ZIF-8 membrane by 233%, and methanol yield by 70%. This work opens new routes for the fabrication of hybrid membranes containing inorganic nanoparticles and MOFs, with potential application not only in catalysis but also in electrochemical, separation, and sensing applications.

Can Advances in Science and Technology Prevent Global Warming? A Critical Review of Limitations and Challenges

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

Huesemann, Michael H.

The most stringent emission scenarios published by the Intergovernmental Panel on Climate Change (IPCC) would result in the stabilization of atmospheric carbon dioxide (CO2) at concentrations of approximately 550 ppm which would produce a global temperature increase of at least 2 C by 2100. Given the large uncertainties regarding the potential risks associated with this degree of global warming, it would be more prudent to stabilize atmospheric CO2 concentrations at or below current levels which, in turn, would require a greater than 20-fold reduction (i.e., ?95%) in per capita carbon emissions in industrialized nations within the next 50 to 100more » years. Using the Kaya equation as a conceptual framework, this paper examines whether CO2 mitigation approaches such as energy efficiency improvements, carbon sequestration, and the development of carbon-free energy sources would be sufficient to bring about the required reduction in per capita carbon emissions without creating unforeseen negative impacts elsewhere. In terms of energy efficiency, large improvements (?5-fold) are in principle possible given aggressive investments in R&D and if market imperfections such as corporate subsidies are removed. However, energy efficiency improvements per se will not result in a reduction in carbon emissions if, as predicted by the IPCC, the size of the global economy has expanded 12-26 fold by 2100. Terrestrial carbon sequestration via reforestation and improved agricultural soil management has many environmental advantages but has only limited CO2 mitigation potential because the global terrestrial carbon sink (ca. 200 Gt C) is small relative to the size of fossil fuel deposits (?4000 Gt C). By contrast, very large amounts of CO2 can potentially be removed from the atmosphere via sequestration in geologic formations and oceans, but carbon storage is not permanent and is likely to create many unpredictable environmental consequences. Renewable solar energy can in theory provide large amounts of carbon-free power. However, biomass and hydroelectric energy can only be marginally expanded and large-scale solar energy installations (i.e., wind, photovoltaics, and direct thermal) are likely to have significant negative environmental impacts. Expansion of nuclear energy is highly unlikely due to concerns over reactor safety, radioactive waste management, weapons proliferation, and cost. In view of the serious limitations and liabilities of many proposed CO2 mitigation approaches it appears that there remain only few no-regrets options such as drastic energy efficiency improvements, extensive terrestrial carbon sequestration, and cautious expansion of renewable energy generation. These promising CO2 mitigation technologies have the potential to bring about the required 20-fold reduction in per capita carbon emission only if population and economic growth are halted without delay. Thus, addressing the problem of global warming requires not only technological research and development but also a reexamination of core values that mistakenly equate material consumption and economic growth to happiness and well-being.« less

Modeling of sonochemistry in water in the presence of dissolved carbon dioxide.

PubMed

Authier, Olivier; Ouhabaz, Hind; Bedogni, Stefano

2018-07-01

CO 2 capture and utilization (CCU) is a process that captures CO 2 emissions from sources such as fossil fuel power plants and reuses them so that they will not enter the atmosphere. Among the various ways of recycling CO 2 , reduction reactions are extensively studied at lab-scale. However, CO 2 reduction by standard methods is difficult. Sonochemistry may be used in CO 2 gas mixtures bubbled through water subjected to ultrasound waves. Indeed, the sonochemical reduction of CO 2 in water has been already investigated by some authors, showing that fuel species (CO and H 2 ) are obtained in the final products. The aim of this work is to model, for a single bubble, the close coupling of the mechanisms of bubble dynamics with the kinetics of gas phase reactions in the bubble that can lead to CO 2 reduction. An estimation of time-scales is used to define the controlling steps and consequently to solve a reduced model. The calculation of the concentration of free radicals and gases formed in the bubble is undertaken over many cycles to look at the effects of ultrasound frequency, pressure amplitude, initial bubble radius and bubble composition in CO 2 . The strong effect of bubble composition on the CO 2 reduction rate is confirmed in accordance with experimental data from the literature. When the initial fraction of CO 2 in the bubble is low, bubble growth and collapse are slightly modified with respect to simulation without CO 2 , and chemical reactions leading to CO 2 reduction are promoted. However, the peak collapse temperature depends on the thermal properties of the CO 2 and greatly decreases as the CO 2 increases in the bubble. The model shows that initial bubble radius, ultrasound frequency and pressure amplitude play a critical role in CO 2 reduction. Hence, in the case of a bubble with an initial radius of around 5 μm, CO 2 reduction appears to be more favorable at a frequency around 300 kHz than at a low frequency of around 20 kHz. Finally, the industrial application of ultrasound to CO 2 reduction in water would be largely dependent on sonochemical efficiency. Under the conditions tested, this process does not seem to be sufficiently efficient. Copyright © 2018 Elsevier B.V. All rights reserved.

Reducing the cost of Ca-based direct air capture of CO2.

PubMed

Zeman, Frank

2014-10-07

Direct air capture, the chemical removal of CO2 directly from the atmosphere, may play a role in mitigating future climate risk or form the basis of a sustainable transportation infrastructure. The current discussion is centered on the estimated cost of the technology and its link to "overshoot" trajectories, where atmospheric CO2 levels are actively reduced later in the century. The American Physical Society (APS) published a report, later updated, estimating the cost of a one million tonne CO2 per year air capture facility constructed today that highlights several fundamental concepts of chemical air capture. These fundamentals are viewed through the lens of a chemical process that cycles between removing CO2 from the air and releasing the absorbed CO2 in concentrated form. This work builds on the APS report to investigate the effect of modifications to the air capture system based on suggestions in the report and subsequent publications. The work shows that reduced carbon electricity and plastic packing materials (for the contactor) may have significant effects on the overall price, reducing the APS estimate from $610 to $309/tCO2 avoided. Such a reduction does not challenge postcombustion capture from point sources, estimated at $80/tCO2, but does make air capture a feasible alternative for the transportation sector and a potential negative emissions technology. Furthermore, air capture represents atmospheric reductions rather than simply avoided emissions.

Upgraded biogas from municipal solid waste for natural gas substitution and CO2 reduction--a case study of Austria, Italy, and Spain.

PubMed

Starr, Katherine; Villalba, Gara; Gabarrell, Xavier

2015-04-01

Biogas is rich in methane and can be further purified through biogas upgrading technologies, presenting a viable alternative to natural gas. Landfills and anaerobic digestors treating municipal solid waste are a large source of such biogas. They therefore offer an attractive opportunity to tap into this potential source of natural gas while at the same time minimizing the global warming impact resulting from methane emissions in waste management schemes (WMS) and fossil fuel consumption reduction. This study looks at the current municipal solid waste flows of Spain, Italy, and Austria over one year (2009), in order to determine how much biogas is generated. Then it examines how much natural gas could be substituted by using four different biogas upgrading technologies. Based on current waste generation rates, exploratory but realistic WMS were created for each country in order to maximize biogas production and potential for natural gas substitution. It was found that the potential substitution of natural gas by biogas resulting from the current WMS seems rather insignificant: 0.2% for Austria, 0.6% for Italy and 0.3% for Spain. However, if the WMS is redesigned to maximize biogas production, these figures can increase to 0.7% for Austria, 1% for Italy and 2% for Spain. Furthermore, the potential CO2 reduction as a consequence of capturing the biogas and replacing fossil fuel can result in up to a 93% reduction of the annual national waste greenhouse gas emissions of Spain and Italy. Copyright © 2015 Elsevier Ltd. All rights reserved.

Methods to assess geological CO2 storage capacity: Status and best practice

USGS Publications Warehouse

Heidug, Wolf; Brennan, Sean T.; Holloway, Sam; Warwick, Peter D.; McCoy, Sean; Yoshimura, Tsukasa

2013-01-01

To understand the emission reduction potential of carbon capture and storage (CCS), decision makers need to understand the amount of CO2 that can be safely stored in the subsurface and the geographical distribution of storage resources. Estimates of storage resources need to be made using reliable and consistent methods. Previous estimates of CO2 storage potential for a range of countries and regions have been based on a variety of methodologies resulting in a correspondingly wide range of estimates. Consequently, there has been uncertainty about which of the methodologies were most appropriate in given settings, and whether the estimates produced by these methods were useful to policy makers trying to determine the appropriate role of CCS. In 2011, the IEA convened two workshops which brought together experts for six national surveys organisations to review CO2 storage assessment methodologies and make recommendations on how to harmonise CO2 storage estimates worldwide. This report presents the findings of these workshops and an internationally shared guideline for quantifying CO2 storage resources.

CO2 Mineralization and Utilization using Steel Slag for Establishing a Waste-to-Resource Supply Chain.

PubMed

Pan, Shu-Yuan; Chung, Tai-Chun; Ho, Chang-Ching; Hou, Chin-Jen; Chen, Yi-Hung; Chiang, Pen-Chi

2017-12-08

Both steelmaking via an electric arc furnace and manufacturing of portland cement are energy-intensive and resource-exploiting processes, with great amounts of carbon dioxide (CO 2 ) emission and alkaline solid waste generation. In fact, most CO 2 capture and storage technologies are currently too expensive to be widely applied in industries. Moreover, proper stabilization prior to utilization of electric arc furnace slag are still challenging due to its high alkalinity, heavy metal leaching potentials and volume instability. Here we deploy an integrated approach to mineralizing flue gas CO 2 using electric arc furnace slag while utilizing the reacted product as supplementary cementitious materials to establish a waste-to-resource supply chain toward a circular economy. We found that the flue gas CO 2 was rapidly mineralized into calcite precipitates using electric arc furnace slag. The carbonated slag can be successfully utilized as green construction materials in blended cement mortar. By this modulus, the global CO 2 reduction potential using iron and steel slags was estimated to be ~138 million tons per year.

Global change impacts on wheat production along an environmental gradient in south Australia.

PubMed

Reyenga, P J; Howden, S M; Meinke, H; Hall, W B

2001-09-01

Crop production is likely to change in the future as a result of global changes in CO2 levels in the atmosphere and climate. APSIM, a cropping system model, was used to investigate the potential impact of these changes on the distribution of cropping along an environmental transect in south Australia. The effects of several global change scenarios were studied, including: (1) historical climate and CO2 levels, (2) historic climate with elevated CO2 (700 ppm), (3) warmer climate (+2.4 degrees C) +700 ppm CO2, (4) drier climate (-15% summer, -20% winter rainfall) +2.4 degrees C +700 ppm CO2, (5) wetter climate (+10% summer rainfall) +2.4 degrees C +700 ppm CO2 and (6) most likely climate changes (+1.8 degrees C, -8% annual rainfall) +700 ppm CO2. Based on an analysis of the current cropping boundary, a criterion of 1 t/ha was used to assess potential changes in the boundary under global change. Under most scenarios, the cropping boundary moved northwards with a further 240,000 ha potentially being available for cropping. The exception was the reduced rainfall scenario (4), which resulted in a small retreat of cropping from its current extent. However, the impact of this scenario may only be small (in the order of 10,000-20,000 ha reduction in cropping area). Increases in CO2 levels over the current climate record have resulted in small but significant increases in simulated yields. Model limitations are discussed.

Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

PubMed

Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

2017-08-09

Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO2 to formate

NASA Astrophysics Data System (ADS)

Lv, Weixin; Zhou, Jing; Bei, Jingjing; Zhang, Rui; Wang, Lei; Xu, Qi; Wang, Wei

2017-01-01

Electrochemical reduction of carbon dioxide (CO2) to formate is energetically inefficient because high overpotential is required for reduction of CO2 to formate on most traditional catalysts. In this paper, a novel nano-sized Bi-based electrocatalyst deposited on a Cu foil has been synthesized, which can be used as a cathode for electrochemical reduction of CO2 to formate with a low overpotential (0.69 V) and a high selectivity (91.3%). The electrocatalyst can show excellent catalytic performance toward reduction of CO2 which can probably be attributed to the nano-sized structure and the surface oxide layer. The energy efficiency for reduction of CO2 to formate can reach to 50% when an IrxSnyRuzO2/Ti electrode is used as anode, it is one of the highest values found in the literatures and very practicable for sustainable fuel synthesis.

Two-Dimensional N,S-Codoped Carbon/Co 9 S 8 Catalysts Derived from Co(OH) 2 Nanosheets for Oxygen Reduction Reaction

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

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

Investigation of highly active and cost-efficient electrocatalysts for oxygen reduction reaction is of great importance in a wide range of clean energy devices, including fuel cells and metal-air batteries. Herein, the simultaneous formation of Co9S8 and N,S-codoped carbon was achieved in a dual templates system. First, Co(OH)2 nanosheets and tetraethyl orthosilicate were utilized to direct the formation of two-dimensional carbon precursors, which were then dispersed into thiourea solution. After subsequent pyrolysis and templates removal, N/S-codoped porous carbon sheets confined Co9S8 catalysts (Co9S8/NSC) were obtained. Owing to the morphological and compositional advantages as well as the synergistic effects, the resultant Co9S8/NSCmore » catalysts with modified doping level and pyrolysis degree exhibit superior ORR catalytic activity and long-term stability compared with the state-of-the-art Pt/C catalyst in alkaline media. Remarkably, the as-prepared carbon composites also reveal exceptional tolerance of methanol, indicating their potential applications in fuel cells.« less

Reduction of CO2 and orbital debris: can CO2 emission trading principles be applied to debris reduction?

NASA Astrophysics Data System (ADS)

Orlando, Giovanni; Kinnersley, Mark; Starke, Juergen; Hugel, Sebastian; Hartner, Gloria; Singh, Sanjay; Loubiere, Vincent; Staebler, Dominik-Markus; O'Brien-Organ, Christopher; Schwindt, Stefan; Serreau, Francois; Sharma, Mohit

In the past years global pollution and the specific situation of global warming changes have been strongly influencing public opinion and thus obliged politicians to initiate/ negotiate in-ternational agreements to control, avoid or at least reduce the impact of CO2 emissions e.g. The Kyoto Protocol (1997) and the International Copenhagen conference on Climate Change (2009). In the orbital debris area the collision between the Iridium33 and Cosmos 2251 satel-lites in 2009 has again pushed to the forefront the discussion of the space pollution by space debris and the increasing risk of critical and catastrophic events during the nominal life time of space objects. It is shown by simulations that for Low Earth Orbits the critical debris situation is already achieved and the existing space objects will probably produce sufficient space debris elements -big enough -to support the cascade effect (Kessler Syndrome). In anal-ogy with CO2 emissions, potential recommendations / regulations to reduce the production of Space Debris or its permanence in orbit, are likely to open new markets involving Miti-gation and Removal of Space Debris. The principle approach for the CO2 emission trading model will be investigated and the applicability for the global space debris handling will be analysed. The major differences of the two markets will be derived and the consequences in-dicated. Potential alternative solutions will be proposed and discussed. For the example of the CO2 emission trading principles within EU and worldwide legal conditions for space debris (national / international laws and recommendations) will be considered as well as the commer-cial approach from the controlled situation of dedicated orders to a free / competitive market in steps. It is of interest to consider forms of potential industrial organisations and interna-tional co-operations to react on a similar architecture for the debris removal trading including incentives and penalties for the different potential customers as satellite operators, agencies or international organisations Giovanni.Orlando@astrium.eads.net Tel.: +49-421-539-4032 juergen.starke@astrium.eads.net Tel.: +49-421-539-4573

One-pot electrodeposition of cobalt flower-decorated silver nanotrees for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Cho, Yun-Bin; Moon, Sinyoung; Lee, Chongmok; Lee, Youngmi

2017-02-01

In this paper, we demonstrate a simple fabrication of bimetallic silver (Ag) and cobalt (Co) nanostructures (AgCo) with various Ag to Co relative contents via electrochemical co-deposition. A series of AgCo catalysts was electrodeposited on glassy carbon (GC) electrodes at -0.57 V vs. SCE in the deposition solutions, containing Ag precursor, Co precursor, Triton X-100, and 0.3 M KNO3 aqueous solution, with various Ag to Co precursor concentration ratios (1:x, x was varied from 3 to 11). The films, deposited with the total deposition charge of 0.042C, were denoted as Ag1Cox. SEM and TEM analyses showed that Ag1Cox formed a structure consisted of flower-like Co grown on tree-like Ag backbones while it had more Co flowers with a greater x. The ORR activities were examined in 0.1 M NaOH solution with rotating disk electrode (RDE) voltammetry and Ag1Co7 showed the best catalytic activity. The co-deposition mechanism was further investigated by varying the deposition time of Ag1Co7. At the early stage of deposition, Ag-tree branches were formed predominantly, followed by the growth of flower-like Co nanostructures on the Ag nanotrees: More Co flowers were produced on Ag backbones with longer deposition time, being attributed to both a less negative reduction potential of Ag+ to Ag than Co2+ to Co and promoted Co2+ reduction on the initially formed Ag surface. Ag1Co7 electrodeposited for 200 s, consisted of ∼14% Co, showed the greatest ORR catalytic activity which was better or comparable to noble metal Pt.

Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan; Graves, Christopher

2018-01-01

Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate the problem, but only to a certain extent. This work shows that a typical SOEC stack converting CO2 to CO and O2 is limited to as little as 15-45% conversion due to risk of carbon formation. Furthermore, cells operated in CO2-electrolysis mode are poisoned by reactant gases containing ppb-levels of sulfur, in contrast to ppm-levels for operation in fuel cell mode.

Cocatalysts in Semiconductor-based Photocatalytic CO2 Reduction: Achievements, Challenges, and Opportunities.

PubMed

Ran, Jingrun; Jaroniec, Mietek; Qiao, Shi-Zhang

2018-02-01

Ever-increasing fossil-fuel combustion along with massive CO 2 emissions has aroused a global energy crisis and climate change. Photocatalytic CO 2 reduction represents a promising strategy for clean, cost-effective, and environmentally friendly conversion of CO 2 into hydrocarbon fuels by utilizing solar energy. This strategy combines the reductive half-reaction of CO 2 conversion with an oxidative half reaction, e.g., H 2 O oxidation, to create a carbon-neutral cycle, presenting a viable solution to global energy and environmental problems. There are three pivotal processes in photocatalytic CO 2 conversion: (i) solar-light absorption, (ii) charge separation/migration, and (iii) catalytic CO 2 reduction and H 2 O oxidation. While significant progress is made in optimizing the first two processes, much less research is conducted toward enhancing the efficiency of the third step, which requires the presence of cocatalysts. In general, cocatalysts play four important roles: (i) boosting charge separation/transfer, (ii) improving the activity and selectivity of CO 2 reduction, (iii) enhancing the stability of photocatalysts, and (iv) suppressing side or back reactions. Herein, for the first time, all the developed CO 2 -reduction cocatalysts for semiconductor-based photocatalytic CO 2 conversion are summarized, and their functions and mechanisms are discussed. Finally, perspectives in this emerging area are provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A robust one-compartment fuel cell with a polynuclear cyanide complex as a cathode for utilizing H2O2 as a sustainable fuel at ambient conditions.

PubMed

Yamada, Yusuke; Yoneda, Masaki; Fukuzumi, Shunichi

2013-08-26

A robust one-compartment H2O2 fuel cell, which operates without membranes at room temperature, has been constructed by using a series of polynuclear cyanide complexes that contain Fe, Co, Mn, and Cr as cathodes, in sharp contrast to conventional H2 and MeOH fuel cells, which require membranes and high temperatures. A high open-circuit potential of 0.68 V was achieved by using Fe3[{Co(III)(CN)6}2] on a carbon cloth as the cathode and a Ni mesh as the anode of a H2O2 fuel cell by using an aqueous solution of H2O2 (0.30  M, pH 3) with a maximum power density of 0.45 mW cm(-2). The open-circuit potential and maximum power density of the H2O2 fuel cell were further increased to 0.78 V and 1.2 mW cm(-2), respectively, by operation under these conditions at pH 1. No catalytic activity of Co3[{Co(III)(CN)6}2] and Co3[{Fe(III)(CN)6}2] towards H2O2 reduction suggests that the N-bound Fe ions are active species for H2O2 reduction. H2O2 fuel cells that used Fe3[{Mn(III)(CN)6}2] and Fe3[{Cr(III)(CN)6}2] as the cathode exhibited lower performance compared with that using Fe3[{Co(III)(CN)6}2] as a cathode, because ligand isomerization of Fe3[{M(III)(CN)6}2] into (FeM2)[{Fe(II)(CN)6}2] (M = Cr or Mn) occurred to form inactive Fe-C bonds under ambient conditions, whereas no ligand isomerization of Fe3[{Co(III)(CN)6}2] occurred under the same reaction conditions. The importance of stable Fe(2+)-N bonds was further indicated by the high performance of the H2O2 fuel cells with Fe3[{Ir(III)(CN)6}2] and Fe3[{Rh(III)(CN)6}2], which also contained stable Fe(2+)-N bonds. The stable Fe(2+)-N bonds in Fe3[{Co(III)(CN)6}2], which lead to high activity for the electrocatalytic reduction of H2O2, allow Fe3[{Co(III)(CN)6}2] to act as a superior cathode in one-compartment H2O2 fuel cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synergy of rising nitrogen depositions and atmospheric CO2 on land carbon uptake moderately offsets global warming

NASA Astrophysics Data System (ADS)

Churkina, Galina; Brovkin, Victor; von Bloh, Werner; Trusilova, Kristina; Jung, Martin; Dentener, Frank

2009-12-01

Increased carbon uptake of land in response to elevated atmospheric CO2 concentration and nitrogen deposition could slow down the rate of CO2 increase and facilitate climate change mitigation. Using a coupled model of climate, ocean, and land biogeochemistry, we show that atmospheric nitrogen deposition and atmospheric CO2 have a strong synergistic effect on the carbon uptake of land. Our best estimate of the global land carbon uptake in the 1990s is 1.34 PgC/yr. The synergistic effect could explain 47% of this carbon uptake, which is higher than either the effect of increasing nitrogen deposition (29%) or CO2 fertilization (24%). By 2030, rising carbon uptake on land has a potential to reduce atmospheric CO2 concentration by about 41 ppm out of which 16 ppm reduction would come from the synergetic response of land to the CO2 and nitrogen fertilization effects. The strength of the synergy depends largely on the cooccurrence of high nitrogen deposition regions with nonagricultural ecosystems. Our study suggests that reforestation and sensible ecosystem management in industrialized regions may have larger potential for climate change mitigation than anticipated.

Formation of CO2, H2 and condensed carbon from siderite dissolution in the 200-300 °C range and at 50 MPa

NASA Astrophysics Data System (ADS)

Milesi, Vincent; Guyot, François; Brunet, Fabrice; Richard, Laurent; Recham, Nadir; Benedetti, Marc; Dairou, Julien; Prinzhofer, Alain

2015-04-01

Laboratory experiments were conducted to investigate the chemical processes governing the carbon speciation associated to hydrothermal decomposition of siderite. Experiments were carried out in sealed gold capsules using synthetic siderite and deionised water. The samples were reacted at 200 and 300 °C, under a pressure of 50 MPa. Siderite dissolved to reach the 3FeCO3 + H2O = Fe3O4 + 3CO2 + H2 equilibrium and magnetite, Fe3O4, was produced accordingly. The gas phase was dominated by CO2, H2 and CH4, the latter being in strong thermodynamic disequilibrium with CO2. Contrary to the other gas products, H2 concentration was found to decrease with run duration. TEM observations showed the occurrence of condensed carbon phases at the surfaces of magnetite and residual siderite grains. Thermodynamic calculations predict the formation of condensed carbon in the experiments according to the reaction: CO2 + 2H2 ⇒ C + 2H2O, which accounted for the observed H2 concentration decrease up to the point where H2 and CO2 activities were buffered by the graphite-siderite-magnetite assemblage. The well-organized structure of the carbon coating around magnetite emphasizes the high catalytic potential of magnetite surface for carbon reduction and polymerization. The formation of such C-rich phases may represent a potential source of CH4 by hydrogenation. On the other hand, the catalysis of Fischer-Tropsch type reactions may be poisoned by the presence of carbon coating on mineral surfaces. In any case, this study also demonstrates that abiotic H2 generation by water reduction, widely studied in recent years in ultrabasic contexts, can also occur in sedimentary contexts where siderite is present. We show that, in the latter case, natural H2 concentration will be buffered by a condensed carbon phase associated with magnetite.

A Mechanistic Study of CO 2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy

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

Flynn, Kristen

2015-08-18

Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played duringmore » the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.« less

A Mechanistic Study of CO 2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

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

Flynn, Kristen

2015-08-19

Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played duringmore » the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.« less

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures

PubMed Central

Zhang, Xing; Wu, Zishan; Zhang, Xiao; Li, Liewu; Li, Yanyan; Xu, Haomin; Li, Xiaoxiao; Yu, Xiaolu; Zhang, Zisheng; Liang, Yongye; Wang, Hailiang

2017-01-01

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm−2 and a turnover frequency of 4.1 s−1 at the overpotential of 0.52 V in a near-neutral aqueous solution. PMID:28272403

Evaluating the CO 2 emissions reduction potential and cost of power sector re-dispatch

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

Steinberg, Daniel C.; Bielen, David A.; Townsend, Aaron

Prior studies of the U.S. electricity sector have recognized the potential to reduce carbon dioxide (CO2) emissions by substituting generation from coal-fired units with generation from under-utilized and lower-emitting natural gas-fired units; in fact, this type of 're-dispatch' was invoked as one of the three building blocks used to set the emissions targets under the Environmental Protection Agency's Clean Power Plan. Despite the existence of surplus natural gas capacity in the U.S., power system operational constraints not often considered in power sector policy analyses, such as transmission congestion, generator ramping constraints, minimum generation constraints, planned and unplanned generator outages, andmore » ancillary service requirements, could limit the potential and increase the cost of coal-to-gas re-dispatch. Using a highly detailed power system unit commitment and dispatch model, we estimate the maximum potential for re-dispatch in the Eastern Interconnection, which accounts for the majority of coal capacity and generation in the U.S. Under our reference assumptions, we find that maximizing coal-to-gas re-dispatch yields emissions reductions of 230 million metric tons (Mt), or 13% of power sector emissions in the Eastern Interconnection, with a corresponding average abatement cost of $15-$44 per metric ton of CO2, depending on the assumed supply elasticity of natural gas.« less

Will Transition of Staple Food Strategy in China Really Mitigate Global Climate Change?

NASA Astrophysics Data System (ADS)

Liu, B.; Zhao, D.

2017-12-01

With the increase in agricultural demand, reducing greenhouse gas (GHG) emissions is a vital challenge in mitigating climate change. Potato staple food strategy in China introduced by Ministry of Agriculture in 2015 is to gradually adjust staple food structure, which provides an opportunity to meet with the challenge. Apart from staple food structure, difference on energy, material input, geography, and crop management are essential to determine agriculture's contribution to climate change. In this study, we conduct a life cycle analysis of four staple foods in China, namely rice, wheat, maize, and potato, to develop crop-specific estimates of GHG emissions and GHG intensity by using `Production intensity' (carbon dioxide equivalent emissions per kilocalorie produced), to help us understand potential synergies and frictions between food producing and climate mitigation. Data used in this study is on city / province levels if city level is unavailable in 2015. First, we evaluate GHG reductions due to transition of staple food structure in China. Staple food GHG emissions in China are 546.90 Tg CO2e yr-1 in 2015, with 47.6%, 21.9%, 27.3% and 3.2% from rice, wheat, maize and potato. Mean production intensity of staple food is 0.45 Mg CO2e M kcal-1 in 2015. Maize leads the intensity with 0.77 Mg CO2e M kcal-1, followed by rice (0.49 Mg CO2e M kcal-1), wheat (0.28 Mg CO2e M kcal-1) and potato (0.24 Mg CO2e M kcal-1). After staple food structure adjustment, 25 Tg CO2e yr-1 (4.2%) reduction will be accomplished in 2020 without any crop management improvement. Further reduction (33.3% - 40.4%) could be achieved with crop management improvement. In addition, because of staple food structure switching, native rice production will decline, which might lead to more export from countries with higher production intensity. Estimated emission leakage from rice import is 30.10 Tg CO2e yr-1, exceeds emission reduction in native China. Therefore, potato staple food strategy could meet the demand for food in China, but it increases risk of global climate change.

Efficient Conversion of CO 2 to CO Using Tin and Other Inexpensive and Easily Prepared Post-Transition Metal Catalysts

DOE PAGES

Medina-Ramos, Jonnathan; Pupillo, Rachel C.; Keane, Thomas P.; ...

2015-02-19

The development of affordable electrocatalysts that can drive the reduction of CO 2 to CO with high selectivity, efficiency, and large current densities is a critical step on the path to production of liquid carbon-based fuels. In this work, we show that inexpensive triflate salts of Sn 2+, Pb 2+, Bi 3+, and Sb 3+ can be used as precursors for the electrodeposition of CO 2 reduction cathode materials from MeCN solutions, providing a general and facile electrodeposition strategy, which streamlines catalyst synthesis. The ability of these four platforms to drive the formation of CO from CO 2 in themore » presence of [BMIM]OTf was probed. The electrochemically prepared Sn and Bi catalysts proved to be highly active, selective, and robust platforms for CO evolution, with partial current densities of j CO = 5-8 mA/cm 2 at applied overpotentials of η < 250 mV. By contrast, the electrodeposited Pb and Sb catalysts do not promote rapid CO generation with the same level of selectivity. The Pb material is only ~10% as active as the Sn and Bi systems at an applied potential of E = -1.95 V and is rapidly passivated during catalysis. The Sb-comprised cathode material shows no activity for conversion of CO 2 to CO under analogous conditions. When taken together, this work demonstrates that 1,3-dialkylimidazoliums can promote CO production, but only when used in combination with an appropriately chosen electrocatalyst material. More broadly, these results suggest that the interactions between CO 2, the imidazolium promoter, and the cathode surface are all critical to the observed catalysis.« less

Metallic nanocatalysts for electrochemical CO2 reduction in aqueous solutions.

PubMed

Wang, Yuanxing; Niu, Cailing; Wang, Dunwei

2018-05-16

How to effectively and efficiently reduce carbon dioxide (CO 2 ) to value-added chemicals represent a frontier in catalysis research. Due to the high activation energy needs and the endothermic nature of CO 2 reduction, the reactions are difficult to carry out. When H 2 O is present, hydrogen evolution reactions (HER) often compete favorably with CO 2 reduction reactions. For these reactions, catalysts are of critical importance to CO 2 reduction. In this article, we review the various metal nanocatalysts for electrochemical CO 2 reduction (ECR) reactions. In recognition of the importance of H 2 O to CO 2 reduction, we focus our discussions on systems in aqueous solutions. Nanostructured metal catalysts are chosen for the discussions because they represent the most effective catalysts for ECR. After a brief introduction of the fundamental principles of ECR, we devote the rest of the article on the discussions of various types of nanostructured metallic catalysts, which are categorized by their compositions and working mechanisms. Lastly, strategies for improving reaction efficiency and selectivity are discussed. Copyright © 2018 Elsevier Inc. All rights reserved.

A Review of CO2 Sequestration Projects and Application in China

PubMed Central

Tang, Yong; Yang, Ruizhi; Bian, Xiaoqiang

2014-01-01

In 2008, the top CO2 emitters were China, United States, and European Union. The rapid growing economy and the heavy reliance on coal in China give rise to the continued growth of CO2 emission, deterioration of anthropogenic climate change, and urgent need of new technologies. Carbon Capture and sequestration is one of the effective ways to provide reduction of CO2 emission and mitigation of pollution. Coal-fired power plants are the focus of CO2 source supply due to their excessive emission and the energy structure in China. And over 80% of the large CO2 sources are located nearby storage reservoirs. In China, the CO2 storage potential capacity is of about 3.6 × 109 t for all onshore oilfields; 30.483 × 109 t for major gas fields between 900 m and 3500 m of depth; 143.505 × 109 t for saline aquifers; and 142.67 × 109 t for coal beds. On the other hand, planation, soil carbon sequestration, and CH4–CO2 reforming also contribute a lot to carbon sequestration. This paper illustrates some main situations about CO2 sequestration applications in China with the demonstration of several projects regarding different ways of storage. It is concluded that China possesses immense potential and promising future of CO2 sequestration. PMID:25302323

Experimental investigation of biofilm formation within a glass porous medium in the presence of carbon dioxide

NASA Astrophysics Data System (ADS)

Sygouni, Varvara; Manariotis, Ioannis D.; Chrysikopoulos, Constantinos V.

2013-04-01

Capturing CO2 emissions and storing them in properly selected deep geologic formations is considered a promising solution for the reduction of CO2 in the atmosphere. However, if CO2 leakage occurs from geologic storage formations due to permeability increases caused by rock-brine-supercritical CO2 geochemical reactions or reactivation of existing fractures, the impact to groundwater quality could be significant. Dissolved CO2 in groundwater can decrease the pH, which in turn can solubilize undesired heavy metals from the solid matrix with profound and severe implications to public health. Consequently, it is essential to fully understand the potential impact of CO2 to shallow groundwater systems. In this study, a series of visualization experiments in a glass-etched micromodel were performed in order to estimate the effect of CO2 on biofilm formation. All biofilms were developed using Pseudomonas (P.) Putida. Synthetic water saturated with CO2 was injected through the micromodel through an inlet port, and CO2 was measured at the outlet port. The transient growth of the biofilm was monitored by taking high-resolution digital photographs at various times, and the effect of CO2 on biofilm growth was estimated. Furthermore, transient changes of effective permeability and porosity were measured and the effect of solution chemistry (e.g. pH, ionic strength, redox potential) on the rate of biofilm growth was evaluated.

Assessing the health risks of natural CO2 seeps in Italy

PubMed Central

Roberts, Jennifer J.; Wood, Rachel A.; Haszeldine, R. Stuart

2011-01-01

Industrialized societies which continue to use fossil fuel energy sources are considering adoption of Carbon Capture and Storage (CCS) technology to meet carbon emission reduction targets. Deep geological storage of CO2 onshore faces opposition regarding potential health effects of CO2 leakage from storage sites. There is no experience of commercial scale CCS with which to verify predicted risks of engineered storage failure. Studying risk from natural CO2 seeps can guide assessment of potential health risks from leaking onshore CO2 stores. Italy and Sicily are regions of intense natural CO2 degassing from surface seeps. These seeps exhibit a variety of expressions, characteristics (e.g., temperature/flux), and location environments. Here we quantify historical fatalities from CO2 poisoning using a database of 286 natural CO2 seeps in Italy and Sicily. We find that risk of human death is strongly influenced by seep surface expression, local conditions (e.g., topography and wind speed), CO2 flux, and human behavior. Risk of accidental human death from these CO2 seeps is calculated to be 10-8 year-1 to the exposed population. This value is significantly lower than that of many socially accepted risks. Seepage from future storage sites is modeled to be less that Italian natural flux rates. With appropriate hazard management, health risks from unplanned seepage at onshore storage sites can be adequately minimized. PMID:21911398

Data and Summaries for Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-Fired Selective Catalytic Reduction Systems

EPA Pesticide Factsheets

Table 1 summarizes and explanis the Operating Conditions of the SCR Reactor used in the Benzene-Destruction.Table 2 summarizes and explains the Experimental Design and Test Results.Table 3 summarizes and explains the Estimates for Individual Effects and Cross Effects Obtained from the Linear Regression Models for Destruction of C6H6 and Reduction of NO.Fig. 1 shows the Down-flow SCR reactor system in detail.Fig. 2 shows the graphical summary of the Effect of the inlet C6H6 concentration to the SCR reactor on the destruction of C6H6.Fig.3 shows the summary of Carbon mass balance for C6H6 destruction promoted by the V2O5-WO3/TiO2 catalyst.This dataset is associated with the following publication:Lee , C., Y. Zhao, S. Lu, and W.R. Stevens. Catalytic Destruction of a Surrogate Organic Hazardous Air Polutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems. AMERICAN CHEMICAL SOCIETY. American Chemical Society, Washington, DC, USA, 30(3): 2240-2247, (2016).

The researches on energy sustainability in Northern China

NASA Astrophysics Data System (ADS)

Wang, Ping; Zhu, Zhiqiang; Zhang, Shuang

2018-06-01

Energy, which accounts for two-thirds of today's greenhouse gas emissions, is the key to reducing greenhouse gas emissions and slowing global warming. In this paper, the IPCC-recommended reference approach and scenario analysis were applied to evaluate dynamic change of the energy supply and energy-related carbon dioxide emissions within the period of 2000-2025 in Northern China (NC). The results show that energy importing reliance reached 85% in 2015 and the energy structure has become more diversified in NC. In addition, the per-capita CO2 emission is significantly higher while carbon intensity is lower than those of the national average. Under the LC scenario, CO2 emissions begin to fall for the first time in 2022. Hence, if Energy-Saving and Emission-Reduction strategy and regional planning for NC are implemented fully, NC will achieve the national emission reduction targets in 2025 and will have a large CO2 mitigation potential in the future.

Recent progress and perspectives in the photocatalytic CO2 reduction of Ti-oxide-based nanomaterials

NASA Astrophysics Data System (ADS)

Sohn, Youngku; Huang, Weixin; Taghipour, Fariborz

2017-02-01

The conversion of CO2 with H2O to valuable chemicals and fuels is a new solution to current environmental and energy problems, and the high energy barrier of these reactions can be overcome by the input of solar and electrical energy. However, the reduction efficiencies and selectivities of these reactions are insufficient for practical use, and significant effort and strategy are required to overcome the many obstacles preventing the large-scale application of photocatalytic CO2 reduction. This article reviews recent progress in CO2 reduction using titanium oxide-based materials and various strategic factors for increasing photocatalytic efficiency. This article also highlights non-titanium-oxide catalysts, the photoelectrocatalytic reduction of CO2, and other recent review articles concerning the recycling of CO2 to value-added carbon compounds.

Cobalt(IV) corroles as catalysts for the electroreduction of O2: reactions of heterobimetallic dyads containing a face-to-face linked Fe(III) or Mn(III) porphyrin.

PubMed

Kadish, Karl M; Frémond, Laurent; Burdet, Fabien; Barbe, Jean-Michel; Gros, Claude P; Guilard, Roger

2006-04-01

A series of heterobinuclear cofacial porphyrin-corrole dyads containing a Co(IV) corrole linked by one of four different spacers in a face-to-face arrangement with an Fe(III) or Mn(III) porphyrin have been examined as catalysts for the electroreduction of O(2) to H(2)O and/or H(2)O(2) when adsorbed on the surface of a graphite electrode in air-saturated aqueous solutions containing 1M HClO(4). The examined compounds are represented as (PCY)M(III)ClCo(IV)Cl where P is a porphyrin dianion, C is a corrole trianion and Y is a biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or anthracene (A) spacer. The catalytic behavior of the seven investigated dyads in the two heterobimetallic (PCY)MClCoCl series of catalysts is compared on one hand to what was previously reported for related dyads with a single Co(III) corrole macrocycle linked to a free-base porphyrin with the same set of linking bridges, (PCY)H(2)Co, and on the other hand to dicobalt porphyrin-corrole dyads of the form (PCY)Co(2) which were shown to efficiently electrocatalyze the four electron reduction of O(2) at a graphite electrode in acid media. Comparisons between the four series of porphyrin-corrole dyads, (PCY)Co(2), (PCY)H(2)Co, (PCY)FeClCoCl and (PCY)MnClCoCl, show that in all cases the biscobalt dyads catalyze O(2) electroreduction at potentials more positive by an average 110mV as compared to the related series of compounds containing a Co(III) or Co(IV) corrole macrocycle linked to a free-base metalloporphyrin or a metalloporphyrin with an Fe(III) or Mn(III) central metal ion. The data indicates that the E(1/2) values where electrocatalysis is initiated is related to the initial site of electron transfer, which is the Co(III)/Co(II) porphyrin reduction process in the case of (PCY)Co(2) and the Co(IV)/Co(III) corrole reduction in the case of (PCY)MnClCoCl, (PCY)FeClCoCl and (PCY)H(2)Co. The overall data also suggests that the catalytically active form of the biscobalt dyad in (PCY)Co(2) contains a Co(II) porphyrin and a Co(IV) corrole.

Reduction of CO2 Emissions Due to Wind Energy - Methods and Issues in Estimating Operational Emission Reductions

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

Holttinen, Hannele; Kiviluoma, Juha; McCann, John

2015-10-05

This paper presents ways of estimating CO2 reductions of wind power using different methodologies. Estimates based on historical data have more pitfalls in methodology than estimates based on dispatch simulations. Taking into account exchange of electricity with neighboring regions is challenging for all methods. Results for CO2 emission reductions are shown from several countries. Wind power will reduce emissions for about 0.3-0.4 MtCO2/MWh when replacing mainly gas and up to 0.7 MtCO2/MWh when replacing mainly coal powered generation. The paper focuses on CO2 emissions from power system operation phase, but long term impacts are shortly discussed.

Carbon Dioxide Removal and Conversion to Ocean Alkalinity: Why and How

NASA Astrophysics Data System (ADS)

Rau, G. H.

2014-12-01

Drastic reduction in anthropogenic CO2 emissions is the most obvious way to stabilize atmospheric CO2. However, there is growing risk that effective emissions reduction policies and technologies will not engage soon enough to avoid significant CO2-induced climate and ocean acidification impacts. This realization has lead to increased interest (e.g., IPCC AR5, 2014; NRC/NAS, 2014) in the possibility of pro-actively increasing CO2 removal (CDR) from the atmosphere above the 55% of our emissions that are already removed from air by natural land and ocean processes. While a variety of biotic, abiotic, and hybrid CDR methods have been proposed, those involving geochemistry have much to recommend them. These methods employ the same geochemical reactions that naturally and effectively remove excess planetary CO2 and neutralize ocean acidity on geologic time scales. These reactions proceed when the hydrosphere, acidified by excess air CO2, contacts and reacts with carbonate and silicate minerals (>90% of the Earth's crust), producing dissolved bicarbonates and carbonates, i.e., ocean alkalinity. This alkalinity is eventually removed and the excess carbon stored via carbonate precipitation. So while the importance and global effectiveness of such reactions are not in question, it remains to be seen if this very slow, natural CDR could be safely and cost-effectively accelerated to help manage air CO2 levels on human rather than geologic time scales. Various terrestrial and marine, geochemistry-based CDR methods will be reviewed including: 1) the addition of minerals to soils and the ocean, 2) removal of CO2 from waste streams, esp. from biomass energy, via wet mineral contacting, and 3) the production and use of mineral derivatives, e.g. oxides or hydroxides, as CDR agents. The additional potential environmental benefits (e.g., reversal of ocean carbonate saturation loss) and impacts (e.g., increased mineral extraction), as well as potential economics will also be discussed.

Fixation of carbon dioxide by a hydrogen-oxidizing bacterium for value-added products.

PubMed

Yu, Jian

2018-06-09

With rapid technology progress and cost reduction, clean hydrogen from water electrolysis driven by renewable powers becomes a potential feedstock for CO 2 fixation by hydrogen-oxidizing bacteria. Cupriavidus necator (formally Ralstonia eutropha), a representative member of the lithoautotrophic prokaryotes, is a promising producer of polyhydroxyalkanoates and single cell proteins. This paper reviews the fundamental properties of the hydrogen-oxidizing bacterium, the metabolic activities under limitation of individual gases and nutrients, and the value-added products from CO 2 , including the products with large potential markets. Gas fermentation and bioreactor safety are discussed for achieving high cell density and high productivity of desired products under chemolithotrophic conditions. The review also updates the recent research activities in metabolic engineering of C. necator to produce novel metabolites from CO 2 .

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

Johnston, Ryne C.; Zhou, Jing; Smith, Jeremy C.

In redox processes in complex transition metal-containing species are often intimately associated with changes in ligand protonation states and metal coordination number. Moreover, a major challenge is therefore to develop consistent computational approaches for computing pH-dependent redox and ligand dissociation properties of organometallic species. Reduction of the Co center in the vitamin B12 derivative aquacobalamin can be accompanied by ligand dissociation, protonation, or both, making these properties difficult to compute accurately. We examine this challenge here by using density functional theory and continuum solvation to compute Co ligand binding equilibrium constants (Kon/off), pKas and reduction potentials for models of aquacobalaminmore » in aqueous solution. We consider two models for cobalamin ligand coordination: the first follows the hexa, penta, tetra coordination scheme for Co III, Co II, and Co I species, respectively, and the second model features saturation of each vacant axial coordination site on Co II and Co I species with a single, explicit water molecule to maintain six directly interacting ligands or water molecules in each oxidation state. Comparing these two coordination schemes in combination with five dispersion-corrected density functionals, we find that the accuracy of the computed properties is largely independent of the scheme used, but including only a continuum representation of the solvent yields marginally better results than saturating the first solvation shell around Co throughout. PBE performs best, displaying balanced accuracy and superior performance overall, with RMS errors of 80 mV for seven reduction potentials, 2.0 log units for five pK as and 2.3 log units for two log K on/off values for the aquacobalamin system. Furthermore, we find that the BP86 functional commonly used in corrinoid studies suffers from erratic behavior and inaccurate descriptions of Co axial ligand binding, leading to substantial errors in predicted pK as and K on/off values. Finally, these findings demonstrate the effectiveness of the present approach for computing electrochemical and thermodynamic properties of a complex transition metal-containing cofactor.« less

Water for electricity in India: A multi-model study of future challenges and linkages to climate change mitigation

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

Srinivasan, Shweta; Kholod, Nazar; Chaturvedi, Vaibhav

This paper provides projections of water withdrawals and consumption for electricity generation in India through 2050. Based on the results from five energy-economic modeling teams, the paper explores the implications of economic growth, power plant cooling policies, and electricity CO 2 emissions reductions on water withdrawals and consumption. To understand how different modeling approaches derive different results for energy-water interactions, the five teams used harmonized assumptions regarding economic and population growth, the distribution of power plants by cooling technologies, and withdrawals and consumption intensities. The multi-model study provides robust results regarding the different but potentially complementary implications of cooling technologymore » policies and efforts to reduce CO 2 emissions. The water implications of CO 2 emissions reductions depend critically on the approach to these reductions. Focusing on wind and solar power reduces consumption and withdrawals, a focus on nuclear power increases both, and a focus on hydroelectric power could increase consumptive losses through evaporation. Policies focused specifically on cooling water can have substantial and complementary impacts.« less

Water for electricity in India: A multi-model study of future challenges and linkages to climate change mitigation

DOE PAGES

Srinivasan, Shweta; Kholod, Nazar; Chaturvedi, Vaibhav; ...

2017-05-05

This paper provides projections of water withdrawals and consumption for electricity generation in India through 2050. Based on the results from five energy-economic modeling teams, the paper explores the implications of economic growth, power plant cooling policies, and electricity CO 2 emissions reductions on water withdrawals and consumption. To understand how different modeling approaches derive different results for energy-water interactions, the five teams used harmonized assumptions regarding economic and population growth, the distribution of power plants by cooling technologies, and withdrawals and consumption intensities. The multi-model study provides robust results regarding the different but potentially complementary implications of cooling technologymore » policies and efforts to reduce CO 2 emissions. The water implications of CO 2 emissions reductions depend critically on the approach to these reductions. Focusing on wind and solar power reduces consumption and withdrawals, a focus on nuclear power increases both, and a focus on hydroelectric power could increase consumptive losses through evaporation. Policies focused specifically on cooling water can have substantial and complementary impacts.« less

Series Bosch System Development

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Evans, Christopher; Mansell, Matt; Swickrath, Michael

2012-01-01

State-of-the-art (SOA) carbon dioxide (CO2) reduction technology for the International Space Station produces methane as a byproduct. This methane is subsequently vented overboard. The associated loss of hydrogen ultimately reduces the mass of oxygen that can be recovered from CO2 in a closed-loop life support system. As an alternative to SOA CO2 reduction technology, NASA is exploring a Series-Bosch system capable of reducing CO2 with hydrogen to form water and solid carbon. This results in 100% theoretical recovery of oxygen from metabolic CO2. In the past, Bosch-based technology did not trade favorably against SOA technology due to a high power demand, low reaction efficiencies, concerns with carbon containment, and large resupply requirements necessary to replace expended catalyst cartridges. An alternative approach to Bosch technology, labeled "Series-Bosch," employs a new system design with optimized multi-stage reactors and a membrane-based separation and recycle capability. Multi-physics modeling of the first stage reactor, along with chemical process modeling of the integrated system, has resulted in a design with potential to trade significantly better than previous Bosch technology. The modeling process and resulting system architecture selection are discussed.

Kinetics of CO2 Reduction over Nonstoichiometric Ceria

PubMed Central

2015-01-01

The kinetics of CO2 reduction over nonstoichimetric ceria, CeO2−δ, a material of high potential for thermochemical conversion of sunlight to fuel, has been investigated for a wide range of nonstoichiometries (0.02 ≤ δ ≤ 0.25), temperatures (693 ≤ T ≤ 1273 K), and CO2 concentrations (0.005 ≤ pCO2 ≤ 0.4 atm). Samples were reduced thermally at 1773 K to probe low nonstoichiometries (δ < 0.05) and chemically at lower temperatures in a H2 atmosphere to prevent particle sintering and probe the effect of higher nonstoichiometries (δ < 0.25). For extents greater than δ = 0.2, oxidation rates at a given nonstoichiometry are hindered for the duration of the reaction, presumably because of near-order changes, such as lattice compression, as confirmed via Raman Spectroscopy. Importantly, this behavior is reversible and oxidation rates are not affected at lower δ. Following thermal reduction at very low δ, however, oxidation rates are an order of magnitude slower than those of chemically reduced samples, and rates monotonically increase with the initial nonstoichiometry (up to δ = 0.05). This dependence may be attributed to the formation of stable defect complexes formed between oxygen vacancies and polarons. When the same experiments are performed with 10 mol % Gd3+ doped ceria, in which defect complexes are less prevalent than in pure ceria, this dependence is not observed. PMID:26693270

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

Using the adsorption chillers for waste heat utilisation from the CCS installation

NASA Astrophysics Data System (ADS)

Sztekler, Karol; Kalawa, Wojciech; Nowak, Wojciech; Stefański, Sebastian; Krzywański, Jarosław; Grabowska, Karolina

2018-06-01

Worldwide tendencies in the scope of environmental protection demonstrate the requirement for the limited carbon dioxide emission, that influences on the development of greenhouse effect. As a result of coal as a basic fuel used in the professional power industry, this industry sector is the greatest CO2 polluter and it means that works on the reduction of carbon dioxide in such industry are completely justified. In the IPSEpro programming environment, a reference block model for a conventional coal power station was elaborated, including the CO2 separation unit basing on the adsorption methods with the CO2 preparation installation to liquid state. Simulation researches were conducted with means of numeric techniques, that enabled the system analysis for the CO2 separation unit with the CO2 preparation system to the liquid state, as well as analysis was made for the use of chiller systems, basing on the adsorption technology for waste heat use originating from the compression of CO2 in a cascade system, as well as for potential opportunities for further exploitation of the produced chilled water in the CCS cycle. We analysed in these papers the opportunities for chiller systems application, based on the adsorption chillers in the CCS installation used for the reduction of CO2 emission in the coal power station and its influence on the operation of a power station cycle.

Pyrolyzed binuclear-cobalt-phthalocyanine as electrocatalyst for oxygen reduction reaction in microbial fuel cells.

PubMed

Li, Baitao; Wang, Mian; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

2015-10-01

A novel platinum (Pt)-free cathodic materials binuclear-cobalt-phthalocyanine (Bi-CoPc) pyrolyzed at different temperatures (300-1000 °C) were examined as the oxygen reduction reaction (ORR) catalysts, and compared with unpyrolyzed Bi-CoPc/C and Pt cathode in single chamber microbial fuel cells (SCMFCs). The results showed that the pyrolysis process increased the nitrogen abundance on Bi-CoPc and changed the nitrogen types. The Bi-CoPc pyrolyzed at 800 °C contained a significant amount of pyrrolic-N, and exhibited a high electrochemical catalytic activity. The power density and current density increased with temperature: Bi-CoPc/C-800 > Bi-CoPc/C-1000 > Bi-CoPc/C-600 > Bi-CoPc/C-300 > Bi-CoPc/C. The SCMFC with Bi-CoPc/C-800 cathode had a maximum power density of 604 mW m(-2). The low cost Bi-CoPc compounds developed in this study showed a potential in air-breathing MFC systems, with the proper pyrolysis temperature being chosen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hybrid photosynthesis-powering biocatalysts with solar energy captured by inorganic devices.

PubMed

Zhang, Tian; Tremblay, Pier-Luc

2017-01-01

The biological reduction of CO 2 driven by sunlight via photosynthesis is a crucial process for life on earth. However, the conversion efficiency of solar energy to biomass by natural photosynthesis is low. This translates in bioproduction processes relying on natural photosynthesis that are inefficient energetically. Recently, hybrid photosynthetic technologies with the potential of significantly increasing the efficiency of solar energy conversion to products have been developed. In these systems, the reduction of CO 2 into biofuels or other chemicals of interest by biocatalysts is driven by solar energy captured with inorganic devices such as photovoltaic cells or photoelectrodes. Here, we explore hybrid photosynthesis and examine the strategies being deployed to improve this biotechnology.

Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

PubMed

Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

2016-05-23

Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coenzyme Q(1) as a probe for mitochondrial complex I activity in the intact perfused hyperoxia-exposed wild-type and Nqo1-null mouse lung.

PubMed

Bongard, Robert D; Myers, Charles R; Lindemer, Brian J; Baumgardt, Shelley; Gonzalez, Frank J; Merker, Marilyn P

2012-05-01

Previous studies showed that coenzyme Q(1) (CoQ(1)) reduction on passage through the rat pulmonary circulation was catalyzed by NAD(P)H:quinone oxidoreductase 1 (NQO1) and mitochondrial complex I, but that NQO1 genotype was not a factor in CoQ(1) reduction on passage through the mouse lung. The aim of the present study was to evaluate the complex I contribution to CoQ(1) reduction in the isolated perfused wild-type (NQO1(+/+)) and Nqo1-null (NQO1(-)/(-)) mouse lung. CoQ(1) reduction was measured as the steady-state pulmonary venous CoQ(1) hydroquinone (CoQ(1)H(2)) efflux rate during infusion of CoQ(1) into the pulmonary arterial inflow. CoQ(1)H(2) efflux rates during infusion of 50 μM CoQ(1) were not significantly different for NQO1(+/+) and NQO1(-/-) lungs (0.80 ± 0.03 and 0.68 ± 0.07 μmol·min(-1)·g lung dry wt(-1), respectively, P > 0.05). The mitochondrial complex I inhibitor rotenone depressed CoQ(1)H(2) efflux rates for both genotypes (0.19 ± 0.08 and 0.08 ± 0.04 μmol·min(-1)·g lung dry wt(-1) for NQO1(+/+) and NQO1(-/-), respectively, P < 0.05). Exposure of mice to 100% O(2) for 48 h also depressed CoQ(1)H(2) efflux rates in NQO1(+/+) and NQO1(-/-) lungs (0.43 ± 0.03 and 0.11 ± 0.04 μmol·min(-1)·g lung dry wt(-1), respectively, P < 0.05 by ANOVA). The impact of rotenone or hyperoxia on CoQ(1) redox metabolism could not be attributed to effects on lung wet-to-dry weight ratios, perfusion pressures, perfused surface areas, or total venous effluent CoQ(1) recoveries, the latter measured by spectrophotometry or mass spectrometry. Complex I activity in mitochondria-enriched lung fractions was depressed in hyperoxia-exposed lungs for both genotypes. This study provides new evidence for the potential utility of CoQ(1) as a nondestructive indicator of the impact of pharmacological or pathological exposures on complex I activity in the intact perfused mouse lung.

Studies on redox H 2-CO 2 cycle on CoCr xFe 2- xO 4

NASA Astrophysics Data System (ADS)

Ma, Ling Juan; Chen, Lin Shen; Chen, Song Ying

2009-01-01

Completely reduced CoCr xFe 2-xO 4 can be used to decompose CO 2. It was found that for pure CoFe 2O 4 there is no FeO formation in the first step while there is formation in the second step. For CoCr 0.08Fe 2-0.08O 4, there is no FeO formed in all the oxidation process, because of effect of Cr 3+. Pure CoFe 2O 4 was destroyed at the first reaction cycle of H 2 reduction and CO 2 oxidation, while doped Cr 3+ spinel CoCr 0.08Fe 1.92O 4 showed good stability. The results from H 2-TG, CO 2-TG and XRD show that the addition of Cr 3+ to CoFe 2O 4 can inhibit the increasing of crystallite size and the sintering of alloy. Most importantly, the CoCr 0.08Fe 1.92O 4 can be used to decompose CO 2 repeatedly, implying that it is a potential catalyst for dealing with the CO 2 as a 'green house effect' gas.

Evaluation of a staged fuel combustor for turboprop engines

NASA Technical Reports Server (NTRS)

Verdouw, A. J.

1976-01-01

Proposed EPA emission regulations require emission reduction by 1979 for various gas turbine engine classes. Extensive combustion technology advancements are required to meet the proposed regulations. The T56 turboprop engine requires CO, UHC, and smoke reduction. A staged fuel combustor design was tested on a combustion rig to evaluate emission reduction potential in turboprop engines from fuel zoning. The can-type combustor has separately fueled-pilot and main combustion zones in series. The main zone fueling system was arranged for potential incorporation into the T56 with minor or no modifications to the basic engine. Three combustor variable geometry systems were incorporated to evaluate various airflow distributions. Emission results with fixed geometry operation met all proposed EPA regulations over the EPA LTO cycle. CO reduction was 82 percent, UHC reduction was 96 percent, and smoke reduction was 84 percent. NOx increased 14 percent over the LTO cycle. At high power, NOx reduction was 40 to 55 percent. This NOx reduction has potential application to stationary gas turbine powerplants which have different EPA regulations.

Electrochemical Reduction of Protic Supercritical CO2 on Copper Electrodes.

PubMed

Melchaeva, Olga; Voyame, Patrick; Bassetto, Victor Costa; Prokein, Michael; Renner, Manfred; Weidner, Eckhard; Petermann, Marcus; Battistel, Alberto

2017-09-22

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO 2 (scCO 2 ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose. Therefore, the focus of this study was on the electrochemical reduction of scCO 2 . The conductivity of scCO 2 was increased through the addition of supporting electrolyte and a cosolvent (acetonitrile). Furthermore, the addition of protic solutions of different pH to scCO 2 was investigated. 1 m H 2 SO 4 , trifluoroethanol, H 2 O, KOH, and CsHCO 3 solutions were used to determine the effect on current density, faradaic efficiency, and selectivity of the scCO 2 reduction. The reduction of scCO 2 to methanol and ethanol are reported for the first time. However, methane and ethylene were not observed. Additionally, corrosion of the Cu electrode was noticed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

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

Zhang, Sheng; Kang, Peng; Bakir, Mohammed

2015-12-14

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. Themore » origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.« less

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

PubMed Central

Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M.; Dares, Christopher J.; Meyer, Thomas J.

2015-01-01

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices. PMID:26668386

Comparison of air pollutant emissions and household air quality in rural homes using improved wood and coal stoves

NASA Astrophysics Data System (ADS)

Du, Wei; Shen, Guofeng; Chen, Yuanchen; Zhu, Xi; Zhuo, Shaojie; Zhong, Qirui; Qi, Meng; Xue, Chunyu; Liu, Guangqing; Zeng, Eddy; Xing, Baoshan; Tao, Shu

2017-10-01

Air pollutant emissions, fuel consumption, and household air pollution were investigated in rural Hubei, central China, as a revisited evaluation of an intervention program to replace coal use by wood in gasifier stoves. Measured emission factors were comparable to the results measured two years ago when the program was initiated. Coal combustion produced significantly higher emissions of CO2, CH4, and SO2 compared with wood combustion; however, wood combustion in gasifier stoves had higher emissions of primary PM2.5 (particles with diameter less than 2.5 μm), Elemental Carbon (EC) and Organic Carbon (OC). In terms of potential impacts on climate, although the use of wood in gasifier stoves produced more black carbon (6.37 vs 910 gCO2e per day per capita from coal and wood use) and less SO2 (-684 vs -312), obvious benefits could be obtained owing to greater OC emissions (-15.4 vs -431), fewer CH4 emissions (865 vs 409) and, moreover, a reduction of CO2 emissions. The total GWC100 (Global Warming Potential over a time horizon of 100 years) would decrease by approximately 90% if coal use were replaced with renewable wood burned in gasifier stoves. However, similar levels of ambient particles and higher indoor OC and EC were found at homes using wood gasifier stoves compared to the coal-use homes. This suggests critical investigations on potential health impacts from the carbon-reduction intervention program.

The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface

PubMed Central

Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, MW; Liu, Li-Min

2016-01-01

CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2− anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

SGLT2 inhibitors: their potential reduction in blood pressure.

PubMed

Maliha, George; Townsend, Raymond R

2015-01-01

The sodium glucose co-transporter 2 (SGLT2) inhibitors represent a promising treatment option for diabetes and its common comorbidity, hypertension. Emerging data suggests that the SGLT2 inhibitors provide a meaningful reduction in blood pressure, although the precise mechanism of the blood pressure drop remains incompletely elucidated. Based on current data, the blood pressure reduction is partially due to a combination of diuresis, nephron remodeling, reduction in arterial stiffness, and weight loss. While current trials are underway focusing on cardiovascular endpoints, the SGLT2 inhibitors present a novel treatment modality for diabetes and its associated hypertension as well as an opportunity to elucidate the pathophysiology of hypertension in diabetes. Copyright © 2015 American Society of Hypertension. Published by Elsevier Inc. All rights reserved.

Method to reduce CO.sub.2 to CO using plasmon-enhanced photocatalysis

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

Huber, George W.; Upadhye, Aniruddha A.; Kim, Hyung Ju

Described is a method of reducing CO.sub.2 to CO using visible radiation and plasmonic photocatalysts. The method includes contacting CO.sub.2 with a catalyst, in the presence of H.sub.2, wherein the catalyst has plasmonic photocatalytic reductive activity when exposed to radiation having a wavelength between 380 nm and 780 nm. The catalyst, CO.sub.2, and H.sub.2 are exposed to non-coherent radiation having a wavelength between 380 nm and 780 nm such that the catalyst undergoes surface plasmon resonance. The surface plasmon resonance increases the rate of CO.sub.2 reduction to CO as compared to the rate of CO.sub.2 reduction to CO without surfacemore » plasmon resonance in the catalyst.« less

Upgraded biogas from municipal solid waste for natural gas substitution and CO{sub 2} reduction – A case study of Austria, Italy, and Spain

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

Starr, Katherine; Villalba, Gara, E-mail: gara.villalba@uab.es; Sostenipra, Institute de Ciencia i Technologia Ambientals

2015-04-15

Highlights: • Biogas can be upgraded to create biomethane, a substitute to natural gas. • Biogas upgrading was applied to landfills and anaerobic digestors in 3 countries. • Up to 0.6% of a country’s consumption of natural gas could be replaced by biomethane. • Italy could save 46% of the national CO{sub 2} emissions attributed to the waste sector. • Scenarios were created to increase biomethane production. - Abstract: Biogas is rich in methane and can be further purified through biogas upgrading technologies, presenting a viable alternative to natural gas. Landfills and anaerobic digestors treating municipal solid waste are amore » large source of such biogas. They therefore offer an attractive opportunity to tap into this potential source of natural gas while at the same time minimizing the global warming impact resulting from methane emissions in waste management schemes (WMS) and fossil fuel consumption reduction. This study looks at the current municipal solid waste flows of Spain, Italy, and Austria over one year (2009), in order to determine how much biogas is generated. Then it examines how much natural gas could be substituted by using four different biogas upgrading technologies. Based on current waste generation rates, exploratory but realistic WMS were created for each country in order to maximize biogas production and potential for natural gas substitution. It was found that the potential substitution of natural gas by biogas resulting from the current WMS seems rather insignificant: 0.2% for Austria, 0.6% for Italy and 0.3% for Spain. However, if the WMS is redesigned to maximize biogas production, these figures can increase to 0.7% for Austria, 1% for Italy and 2% for Spain. Furthermore, the potential CO{sub 2} reduction as a consequence of capturing the biogas and replacing fossil fuel can result in up to a 93% reduction of the annual national waste greenhouse gas emissions of Spain and Italy.« less

Quantum chemical studies of redox properties and conformational changes of a four-center iron CO2 reduction electrocatalyst† †Electronic supplementary information (ESI) available: XYZ coordinates of energy minimized and transition state structures reported in this paper, as well as wavefunction analyses of CO dissociation from 12–. See DOI: 10.1039/c7sc04342b

PubMed Central

Jang, Hyesu; Qiu, Yudong; Hutchings, Marshall E.; Nguyen, Minh; Berben, Louise A.

2018-01-01

The CO2 reduction electrocatalyst [Fe4N(CO)12]– (abbrev. 1–) reduces CO2 to HCO2– in a two-electron, one-proton catalytic cycle. Here, we employ ab initio calculations to estimate the first two redox potentials of 1– and explore the pathway of a side reaction involving CO dissociation from 13–. Using the BP86 density functional approximation, the redox potentials were computed with a root mean squared error of 0.15 V with respect to experimental data. High temperature Born–Oppenheimer molecular dynamics was employed to discover a reaction pathway of CO dissociation from 13– with a reaction energy of +10.6 kcal mol–1 and an activation energy of 18.8 kcal mol–1; including harmonic free energy terms, this yields ΔGsep = 1.4 kcal mol–1 for fully separated species and ΔG‡ = +17.4 kcal mol–1, indicating CO dissociation is energetically accessible at ambient conditions. The analogous dissociation pathway from 12– has a reaction energy of 22.1 kcal mol–1 and an activation energy of 22.4 kcal mol–1 (ΔGsep = 12.8 kcal mol–1, ΔG‡ = +18.1 kcal mol–1). Our computed harmonic vibrational analysis of [Fe4N(CO)11]3– or 23– reveals a distinct CO-stretching peak red-shifted from the main CO-stretching band, pointing to a possible vibrational signature of dissociation. Multi-reference CASSCF calculations are used to check the assumptions of the density functional approximations that were used to obtain the majority of the results. PMID:29732050

Reviews and syntheses: Calculating the global contribution of coralline algae to total carbon burial

NASA Astrophysics Data System (ADS)

van der Heijden, L. H.; Kamenos, N. A.

2015-11-01

The ongoing increase in anthropogenic carbon dioxide (CO2) emissions is changing the global marine environment and is causing warming and acidification of the oceans. Reduction of CO2 to a sustainable level is required to avoid further marine change. Many studies investigate the potential of marine carbon sinks (e.g. seagrass) to mitigate anthropogenic emissions, however, information on storage by coralline algae and the beds they create is scant. Calcifying photosynthetic organisms, including coralline algae, can act as a CO2 sink via photosynthesis and CaCO3 dissolution and act as a CO2 source during respiration and CaCO3 production on short-term timescales. Long-term carbon storage potential might come from the accumulation of coralline algae deposits over geological timescales. Here, the carbon storage potential of coralline algae is assessed using meta-analysis of their global organic and inorganic carbon production and the processes involved in this metabolism. Net organic and inorganic production were estimated at 330 g C m-2 yr-1 and 900 g CaCO3 m-2 yr-1 respectively giving global organic/inorganic C production of 0.7/1.8 × 109 t C yr-1. Calcium carbonate production by free-living/crustose coralline algae (CCA) corresponded to a sediment accretion of 70/450 mm kyr-1. Using this potential carbon storage for coralline algae, the global production of free-living algae/CCA was 0.4/1.2 × 109 t C yr-1 suggesting a total potential carbon sink of 1.6 × 109 tonnes per year. Coralline algae therefore have production rates similar to mangroves, salt marshes and seagrasses representing an as yet unquantified but significant carbon store, however, further empirical investigations are needed to determine the dynamics and stability of that store.

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

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

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE PAGES

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros; ...

2017-12-06

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

The carbon isotope biogeochemistry of (epsilon)CO2 production in a methanogenic marine sediment

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

To investigate the relationship between sigma(CO2) delta(C-13) values and rates of the dominant remineralization processes at the organic-rich field site of Cape Lookout Bight, NC, the isotopic composition of porewater sigma(CO2) was measured on a seasonal basis. The sigma(CO2) delta(C-13) values varies seasonally in response to changes in rates of sulfate reduction and methanogenesis, the dominant remineralization processes at this site. A tube incubation experiment was also performed to determine the isotopic signature of the sigma(CO2) produced by sulfate reduction and methanogenesis. The delta(C-13) of the sigma(CO2) produced in the sulfate reduction zone determined from the tube incubation was -14.3 plus or minus 1.9, a value enriched in C-13 relative to the labile organic fraction. The C-13-enrichment may be caused by low rates of methanogenesis occurring in the sulfate reduction zone. The delta(C-13) of the sigma(CO2) produced in the methanogenic zone was estimated to be +44 per mil, whereas the co-produced methane was -65 per mil. The fractionation factor for CO2 reduction was calculated to be 1.055, a value in agreement with previous estimates at this site. The measured concentration and delta(C-13) of the sigma(CO2) at Cape Lookout was closely reproduced by a diagenetic model using the measured rates of sulfate reduction and sigma(CO2) production, and the isotopic signature of the sigma(CO2) production in the two biogeochemical zones.

Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

NASA Astrophysics Data System (ADS)

Liu, Jie; Huang, Yan

2018-05-01

Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

Synthesis of Hierarchical Nanoporous Microstructures via the Kirkendall Effect in Chemical Reduction Process

NASA Astrophysics Data System (ADS)

Gao, Ling; Pang, Chao; He, Dafang; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

2015-11-01

A series of novel hierarchical nanoporous microstructures have been synthesized through one-step chemical reduction of micron size Cu2O and Co3O4 particles. By controlling the reduction time, non-porous Cu2O microcubes sequentially transform to nanoporous Cu/Cu2O/Cu dented cubic composites and hollow eightling-like Cu microparticles. The mechanism involved in the complex structural evolution is explained based on oxygen diffusion and Kirkendall effect. The nanoporous Cu/Cu2O/Cu dented cubic composites exhibit superior electrochemical performance as compared to solid Cu2O microcubes. The reduction of nonporous Co3O4 also exhibits a uniform sequential reduction process from nonporous Co3O4 to porous Co3O4/CoO composites, porous CoO, porous CoO/Co composites, and porous foam-like Co particles. Nanoscale channels originate from the particle surface and eventually develop inside the entire product, resulting in porous foam-like Co microparticles. The Kirkendall effect is believed to facilitate the formation of porous structures in both processes.

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

PubMed

Luca, Oana R; Fenwick, Aidan Q

2015-11-01

The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. Copyright © 2015 Elsevier B.V. All rights reserved.

Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface.

PubMed

Singer, David M; Chatman, Shawn M; Ilton, Eugene S; Rosso, Kevin M; Banfield, Jillian F; Waychunas, Glenn A

2012-04-03

Sequestration of uranium (U) by magnetite is a potentially important sink for U in natural and contaminated environments. However, molecular-scale controls that favor U(VI) uptake including both adsorption of U(VI) and reduction to U(IV) by magnetite remain poorly understood, in particular, the role of U(VI)-CO(3)-Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaNO(3); and with or without 0.5 mM CO(3) and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended X-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO(3)](T), denoted here as CO(3)) and calcium (Ca), or in the presence of CO(3) only, coexisting adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both Ca and CO(3), only U(VI) adsorption (VI) occurs. When U reduction occurs, nanoparticulate UO(2) forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO(3) and Ca, U(VI)-CO(3)-Ca ternary surface species develop and U reduction is inhibited. These findings extend the range of conditions under which U(VI)-CO(3)-Ca complexes inhibit U reduction.

New Directions for the Photocatalytic Reduction of CO2: Supramolecular, scCO2 or Biphasic Ionic Liquid-scCO2 Systems

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

Grills, D.C.; Fujita, E.

2010-09-02

There is an urgent need for the discovery of carbon-neutral sources of energy to avoid the consequences of global warming caused by ever-increasing atmospheric CO{sub 2} levels. An attractive possibility is to use CO{sub 2} captured from industrial emissions as a feedstock for the production of useful fuels and precursors such as carbon monoxide and methanol. An active field of research to achieve this goal is the development of catalysts capable of harnessing solar energy for use in artificial photosynthetic processes for CO{sub 2} reduction. Transition-metal complexes are excellent candidates, and it has already been shown that they can bemore » used to reduce CO{sub 2} with high quantum efficiency. However, they generally suffer from poor visible light absorption, short catalyst lifetimes, and poor reaction rates. In this Perspective, the field of photocatalytic CO{sub 2} reduction is introduced, and recent developments that seek to improve the efficiency of such catalytic processes are highlighted, especially CO{sub 2} reduction with supramolecules and molecular systems in supercritical CO{sub 2} (scCO{sub 2}) or biphasic ionic liquid-scCO{sub 2} mixtures.« less

Quantifying and managing regional greenhouse gas emissions: waste sector of Daejeon, Korea.

PubMed

Yi, Sora; Yang, Heewon; Lee, Seung Hoon; An, Kyoung-Jin

2014-06-01

A credible accounting of national and regional inventories for the greenhouse gas (GHG) reduction has emerged as one of the most significant current discussions. This article assessed the regional GHG emissions by three categories of the waste sector in Daejeon Metropolitan City (DMC), Korea, examined the potential for DMC to reduce GHG emission, and discussed the methodology modified from Intergovernmental Panel on Climate Change and Korea national guidelines. During the last five years, DMC's overall GHG emissions were 239 thousand tons CO2 eq./year from eleven public environmental infrastructure facilities, with a population of 1.52 million. Of the three categories, solid waste treatment/disposal contributes 68%, whilst wastewater treatment and others contribute 22% and 10% respectively. Among GHG unit emissions per ton of waste treatment, the biggest contributor was waste incineration of 694 kg CO2 eq./ton, followed by waste disposal of 483 kg CO2 eq./ton, biological treatment of solid waste of 209 kg CO2 eq./ton, wastewater treatment of 0.241 kg CO2 eq./m(3), and public water supplies of 0.067 kg CO2 eq./m(3). Furthermore, it is suggested that the potential in reducing GHG emissions from landfill process can be as high as 47.5% by increasing landfill gas recovery up to 50%. Therefore, it is apparent that reduction strategies for the main contributors of GHG emissions should take precedence over minor contributors and lead to the best practice for managing GHGs abatement. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Elevated CO2 Reduced Floret Death in Wheat Under Warmer Average Temperatures and Terminal Drought

PubMed Central

Dias de Oliveira, Eduardo; Palta, Jairo A.; Bramley, Helen; Stefanova, Katia; Siddique, Kadambot H. M.

2015-01-01

Elevated CO2 often increases grain yield in wheat by enhancing grain number per ear, which can result from an increase in the potential number of florets or a reduction in the death of developed florets. The hypotheses that elevated CO2 reduces floret death rather than increases floret development, and that grain size in a genotype with more grains per unit area is limited by the rate of grain filling, were tested in a pair of sister lines contrasting in tillering capacity (restricted- vs. free-tillering). The hypotheses were tested under elevated CO2, combined with +3°C above ambient temperature and terminal drought, using specialized field tunnel houses. Elevated CO2 increased net leaf photosynthetic rates and likely the availability of carbon assimilates, which significantly reduced the rates of floret death and increased the potential number of grains at anthesis in both sister lines by an average of 42%. The restricted-tillering line had faster grain-filling rates than the free-tillering line because the free-tillering line had more grains to fill. Furthermore, grain-filling rates were faster under elevated CO2 and +3°C above ambient. Terminal drought reduced grain yield in both lines by 19%. Elevated CO2 alone increased the potential number of grains, but a trade-off in yield components limited grain yield in the free-tillering line. This emphasizes the need for breeding cultivars with a greater potential number of florets, since this was not affected by the predicted future climate variables. PMID:26635837

Potential of European 14CO2 observation network to estimate the fossil fuel CO2 emissions via atmospheric inversions

NASA Astrophysics Data System (ADS)

Wang, Yilong; Broquet, Grégoire; Ciais, Philippe; Chevallier, Frédéric; Vogel, Felix; Wu, Lin; Yin, Yi; Wang, Rong; Tao, Shu

2018-03-01

Combining measurements of atmospheric CO2 and its radiocarbon (14CO2) fraction and transport modeling in atmospheric inversions offers a way to derive improved estimates of CO2 emitted from fossil fuel (FFCO2). In this study, we solve for the monthly FFCO2 emission budgets at regional scale (i.e., the size of a medium-sized country in Europe) and investigate the performance of different observation networks and sampling strategies across Europe. The inversion system is built on the LMDZv4 global transport model at 3.75° × 2.5° resolution. We conduct Observing System Simulation Experiments (OSSEs) and use two types of diagnostics to assess the potential of the observation and inverse modeling frameworks. The first one relies on the theoretical computation of the uncertainty in the estimate of emissions from the inversion, known as posterior uncertainty, and on the uncertainty reduction compared to the uncertainty in the inventories of these emissions, which are used as a prior knowledge by the inversion (called prior uncertainty). The second one is based on comparisons of prior and posterior estimates of the emission to synthetic true emissions when these true emissions are used beforehand to generate the synthetic fossil fuel CO2 mixing ratio measurements that are assimilated in the inversion. With 17 stations currently measuring 14CO2 across Europe using 2-week integrated sampling, the uncertainty reduction for monthly FFCO2 emissions in a country where the network is rather dense like Germany, is larger than 30 %. With the 43 14CO2 measurement stations planned in Europe, the uncertainty reduction for monthly FFCO2 emissions is increased for the UK, France, Italy, eastern Europe and the Balkans, depending on the configuration of prior uncertainty. Further increasing the number of stations or the sampling frequency improves the uncertainty reduction (up to 40 to 70 %) in high emitting regions, but the performance of the inversion remains limited over low-emitting regions, even assuming a dense observation network covering the whole of Europe. This study also shows that both the theoretical uncertainty reduction (and resulting posterior uncertainty) from the inversion and the posterior estimate of emissions itself, for a given prior and true estimate of the emissions, are highly sensitive to the choice between two configurations of the prior uncertainty derived from the general estimate by inventory compilers or computations on existing inventories. In particular, when the configuration of the prior uncertainty statistics in the inversion system does not match the difference between these prior and true estimates, the posterior estimate of emissions deviates significantly from the truth. This highlights the difficulty of filtering the targeted signal in the model-data misfit for this specific inversion framework, the need to strongly rely on the prior uncertainty characterization for this and, consequently, the need for improved estimates of the uncertainties in current emission inventories for real applications with actual data. We apply the posterior uncertainty in annual emissions to the problem of detecting a trend of FFCO2, showing that increasing the monitoring period (e.g., more than 20 years) is more efficient than reducing uncertainty in annual emissions by adding stations. The coarse spatial resolution of the atmospheric transport model used in this OSSE (typical of models used for global inversions of natural CO2 fluxes) leads to large representation errors (related to the inability of the transport model to capture the spatial variability of the actual fluxes and mixing ratios at subgrid scales), which is a key limitation of our OSSE setup to improve the accuracy of the monitoring of FFCO2 emissions in European regions. Using a high-resolution transport model should improve the potential to retrieve FFCO2 emissions, and this needs to be investigated.

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.

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

DOE PAGES

Zhang, Chenhao; Yang, Shize; Wu, Jingjie; ...

2018-03-25

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

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

Zhang, Chenhao; Yang, Shize; Wu, Jingjie

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

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

Coker, Eric Nicholas; Rodriguez, Mark A.; Ambrosini, Andrea

Hydrogen and carbon monoxide may be produced using solar-thermal energy in two-stage reactions of water and carbon dioxide, respectively, over certain metal oxide materials. The most active materials observed experimentally for these processes are complex mixtures of ferrite and zirconia based solids, and it is not clear how far the ferrites, the zirconia, or a solid solution between the two participate in the change of oxidation state during the cycling. Identification of the key phases in the redox material that enable splitting is of paramount importance to developing a working model of the materials. A three-pronged approach was adopted here:more » computer modeling to determine thermodynamically favorable materials compositions, bench reactor testing to evaluate materials’ performance, and in-situ characterization of reactive materials to follow phase changes and identify the phases active for splitting. For the characterization and performance evaluation thrusts, cobalt ferrites were prepared by co-precipitation followed by annealing at 1400 °C. An in-situ X-ray diffraction capability was developed and tested, allowing phase monitoring in real time during thermochemical redox cycling. Key observations made for an un-supported cobalt ferrite include: 1) ferrite phases partially reduce to wustite upon heating to 1400 °C in helium; 2) exposing the material to air at 1100 °C causes immediate re-oxidation; 3) the re-oxidized material may be thermally reduced at 1400 °C under inert; 4) exposure of a reduced material to CO 2 results in gradual re-oxidation at 1100 °C, but minimization of background O 2-levels is essential; 5) even after several redox cycles, the lattice parameters of the ferrites remain constant, indicating that irreversible phase separation does not occur, at least over the first five cycles; 6) substituting chemical (hydrogen) reduction for thermal reduction resulted in formation of a CoFe metallic alloy. Materials were also evaluated for their CO 2-splitting performance in bench reactor systems utilizing chemical reduction in place of thermal reduction. These tests lead to the following general conclusions: 1) despite over-reduction of the cobalt ferrite phase to CoFe alloy on chemical reduction, splitting of CO 2 still occurs; 2) the kinetics of chemical reduction follow the sequence: un-supported < ZrO 2-supported < yttria-stabilized ZrO 2 (YSZ)-supported ferrite; 3) ferrite/YSZ re-oxidizes faster than ferrite/ZrO 2 under CO 2 in the range 400 – 700 °C. The temperature and pressure regimes in which the thermal reduction and water-splitting steps are thermodynamically favorable in terms of the enthalpy and entropy of oxide reduction, were determined. These metrics represent a useful design goal for any proposed water-splitting cycle. Applying this theoretical framework to available thermodynamic data, it was shown that none of the 105 binary oxide redox couples that were screened possess both energetically favorable reduction and oxidation steps. However, several driving forces, including low pressure and a large positive solid-state entropy of reduction of the oxide, have the potential to enable thermodynamically-favored two-step cycles.« less

Pt skin on Pd–Co–Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

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

Xiao, Weiping; Zhu, Jing; Han, Lili

Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). A highly active, durable, carbon supported, and monolayer Pt coated Pd–Co–Zn nanoparticle is synthesized via a simple impregnation–reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition–activity volcano curve for the Pd–Co–Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd 8CoZn/C nanoparticles show a substantial enhancement in bothmore » the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd 8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N 2-saturated 0.1 M HClO 4 solution, Pd 8CoZn@Pt/C shows improved mass activity (2.62 A mg -1Pt) and specific activity (4.76 A m -2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O 2-saturated 0.1 M HClO 4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. Our results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.« less

Pt skin on Pd–Co–Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

DOE PAGES

Xiao, Weiping; Zhu, Jing; Han, Lili; ...

2016-07-15

Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). A highly active, durable, carbon supported, and monolayer Pt coated Pd–Co–Zn nanoparticle is synthesized via a simple impregnation–reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition–activity volcano curve for the Pd–Co–Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd 8CoZn/C nanoparticles show a substantial enhancement in bothmore » the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd 8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N 2-saturated 0.1 M HClO 4 solution, Pd 8CoZn@Pt/C shows improved mass activity (2.62 A mg -1Pt) and specific activity (4.76 A m -2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O 2-saturated 0.1 M HClO 4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. Our results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.« less

Co- and defect-rich carbon nanofiber films as a highly efficient electrocatalyst for oxygen reduction

NASA Astrophysics Data System (ADS)

Kim, Il To; Song, Myeong Jun; Shin, Seoyoon; Shin, Moo Whan

2018-03-01

Many efforts are continuously devoted to developing high-efficiency, low-cost, and highly scalable oxygen reduction reaction (ORR) electrocatalysts to replace precious metal catalysts. Herein, we successfully synthesize Co- and defect-rich carbon nanofibers (CNFs) using an efficient heat treatment approach involving the pyrolysis of electrospun fibers at 370 °C under air. The heat treatment process produces Co-decorated CNFs with a high Co mass ratio, enriched pyridinic N, Co-pyridinic Nx clusters, and defect-rich carbon structures. The synergistic effects from composition and structural changes in the designed material increase the number of catalytically active sites for the ORR in an alkaline solution. The prepared Co- and defect-rich CNFs exhibit excellent ORR activities with a high ORR onset potential (0.954 V vs. RHE), a large reduction current density (4.426 mA cm-2 at 0.40 V), and a nearly four-electron pathway. The catalyst also exhibits a better long-term durability than commercial Pt/C catalysts. This study provides a novel hybrid material as an efficient ORR catalyst and important insight into the design strategy for CNF-based hybrid materials as electrochemical electrodes.

Drivers of potential GHG fluxes under bioenergy land use change in the UK

NASA Astrophysics Data System (ADS)

Parmar, Kim; Keith, Aidan M.; Perks, Mike; Rowe, Rebecca; Sohi, Saran; McNamara, Niall

2013-04-01

The greatest contributors to global greenhouse gases (GHG's) are CO2 emissions from fossil fuel use and following land use change (LUC). Globally, soils contain three times more carbon than the atmosphere and have the potential to act as GHG sources or sinks. A significant amount of land may be converted to bioenergy production to help meet UK 2050 renewable energy and GHG emissions reduction targets. This raises considerable sustainability concerns with respect to the effects of LUC on soil carbon (C) conservation and GHG emissions. Forests are a key component in the global C cycle and when managed effectively can reduce atmospheric GHG concentrations. Together with other dedicated bioenergy crops, Short Rotation Forestry (SRF) could be used to meet biomass requirements. SRF is defined as high density plantations of fastgrowing tree species grown on short rotational lengths (8-20 years) for biomass (McKay 2011). As SRF is likely to be an important domestic source of biomass for energy it is imperative that we gain an understanding of the implications for large-scale commercial application on soil C and the GHG balance. We utilized a paired-site approach to investigate how LUC to SRF could potentially alter the underlying processes of soil GHG production and consumption. This work was linked to a wider soil C stock inventory for bioenergy LUC, so our major focus was on changes to soil respiration. Specifically, we examined the relative importance of litter, soil, and microbial properties in determining potential soil respiration, and whether these relationships were consistent at different soil temperatures (10 ° C and 20 ° C). Soils were sampled to a depth of 30 cm from 30 LUC transitions across the UK and incubated under controlled laboratory conditions, with gas samples taken over a seven day enclosure period. CO2, N2O and CH4 gas fluxes were measured by gas chromatography and were examined together with other soil properties measured in the field and laboratory. LUC to SRF resulted in a significant reduction in CO2 fluxes overall at 0-15 cm (on both a soil mass and carbon mass basis). Furthermore, this response of CO2 flux to LUC was similar at both 10 ° C and 20 ° C. Reductions in CO2 flux at 0-15 cm are significantly related to decreased bacterial biomass, as measured by Phospholipid Fatty Acids (PLFA), soil pH and bulk density. These patterns suggest that changes in the quality and quantity of organic inputs under SRF may drive a reduction in soil respiration. While changes in soil C were limited, reduced respiration was supported by the increase in litter C stock under SRF. These findings indicate that LUC to SRF can strengthen the soils potential as a C sink whilst contributing successfully towards meeting GHG emissions reduction targets. This work is based on the Ecosystem Land Use Modelling & Soil Carbon GHG Flux Trial (ELUM) project, which was commissioned and funded by the Energy Technologies Institute (ETI)

Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad

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

Martinez, Jose F.; La Porte, Nathan T.; Mauck, Catherine M.

2017-01-01

The naphthalene-1,4:5,8-bis(dicarboximide) radical anion (NDI -˙), which is easily produced by mild chemical or electrochemical reduction (-0.5 Vvs.SCE), can be photoexcited at wavelengths as long as 785 nm, and has an excited state (NDI -˙*) oxidation potential of -2.1 Vvs.SCE, making it a very attractive choice for artificial photosynthetic systems that require powerful photoreductants, such as CO 2 reduction catalysts. However, once an electron is transferred from NDI -˙* to an acceptor directly bound to it, a combination of strong electronic coupling and favorable free energy change frequently make the back electron transfer rapid. To mitigate this effect, we havemore » designed a molecular triad system comprising an NDI -˙ chromophoric donor, a 9,10-diphenylanthracene (DPA) intermediate acceptor, and a Re(dmb)(CO) 3carbon dioxide reduction catalyst, where dmb is 4,4'-dimethyl-2,2'-bipyridine, as the terminal acceptor. Photoexcitation of NDI -˙ to NDI -˙* is followed by ultrafast reduction of DPA to DPA -˙, which then rapidly reduces the metal complex. The overall time constant for the forward electron transfer to reduce the metal complex is τ = 20.8 ps, while the time constant for back-electron transfer is six orders of magnitude longer, τ = 43.4 μs. Achieving long-lived, highly reduced states of these metal complexes is a necessary condition for their use as catalysts. The extremely long lifetime of the reduced metal complex is attributed to careful tuning of the redox potentials of the chromophore and intermediate acceptor. The NDI -˙–DPA fragment presents many attractive features for incorporation into other photoinduced electron transfer assemblies directed at the long-lived photosensitization of difficult-to-reduce catalytic centers.« less

Oxygen Generation from Carbon Dioxide for Advanced Life Support

NASA Technical Reports Server (NTRS)

Bishop, s. R.; Duncan, K. L.; Hagelin-Weaver, H. E.; Neal, L.; Paul, H. L.; Wachsman, E. D.

2007-01-01

The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.

Thermogravimetric and Magnetic Studies of the Oxidation and Reduction Reaction of SmCoO3 to Nanostructured Sm2O3 and Co

NASA Astrophysics Data System (ADS)

Kelly, Brian; Cichocki, Ronald; Poirier, Gerald; Unruh, Karl

The SmCoO3 to nanostructured Sm2O3 and Co oxidation and reduction reaction has been studied by thermogravimetric analysis (TGA) measurements in forming gas (FG) and inert N2 atmospheres, x-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The TGA measurements showed two clearly resolvable reduction processes when heating in FG, from the initial SmCoO3 phase through an intermediate nanostructured mixture of Sm2O3 and CoO when heated to 330°C for several minutes, and then the conversion of CoO to metallic Co when heated above 500°C. These phases were confirmed by XRD and VSM. Similar measurements in N2 yielded little mass change below 900°C and coupled reduction processes at higher temperatures. Isoconversional measurements of the CoO to Co reduction reaction in FG yielded activation energies above 2eV/atom in the nanostructured system. This value is several times larger than those reported in the literature or obtained by similar measurements of bulk mixtures of Sm2O3 and CoO, suggesting the nanostructuring was the source of the large increase in activation energy.

Effectiveness of Six Improved Cookstoves in Reducing Household Air Pollution and Their Acceptability in Rural Western Kenya

PubMed Central

Pilishvili, Tamara; Loo, Jennifer D.; Schrag, Stephanie; Stanistreet, Debbi; Christensen, Bryan; Yip, Fuyuen; Nyagol, Ronald; Quick, Robert; Sage, Mike; Bruce, Nigel

2016-01-01

Background Household air pollution (HAP) from biomass fuel burning is linked to poor health outcomes. Improved biomass cookstoves (ICS) have the potential to improve HAP. Objectives A pre-/post- intervention study assessed the impact of six ICS on indoor air quality and acceptability of ICS to local users in rural Western Kenya. Methods We measured mean personal and kitchen level concentrations of particulate matter <2.5μm in diameter (PM2.5, μg/m3) and carbon monoxide (CO, ppm) during the 48-hour period of each ICS use in 45 households. We compared these levels to those observed with traditional 3-stone fire (TSF) use. We assessed ICS acceptability through interviews and focus groups. We evaluated association of stove type, fuel use, and factors related to cooking practices with mean kitchen PM2.5 and CO using multivariable regression. Results Stove type, exclusive ICS use (vs. concurrent TSF use), and the amount of fuel used were independently associated with kitchen PM2.5 and CO levels. Reductions (95%CI) in mean PM2.5 compared to TSF, ranged by ICS from 11.9% (-2.8–24.5) to 42.3% (32.3–50.8). Reductions in kitchen CO compared to TSF, ranged by ICS from -5.8% (-21.9–8.2) to 34.5% (23.2–44.1). Mean kitchen PM2.5 ranged from 319μg/m3 to 518μg/m3 by ICS. Women thought ICS were easy to use, more efficient, produced less smoke, and cooked faster, compared to TSF. Women also reported limitations for each ICS. Conclusions We documented reductions in HAP from ICS compared to TSF. The PM2.5 levels with ICS use were still considerably higher than WHO indoor air quality guidelines. Achieving maximal potential of ICS requires adherence to more exclusive use and addressing user reported ICS limitations. PMID:27846224

Effectiveness of Six Improved Cookstoves in Reducing Household Air Pollution and Their Acceptability in Rural Western Kenya.

PubMed

Pilishvili, Tamara; Loo, Jennifer D; Schrag, Stephanie; Stanistreet, Debbi; Christensen, Bryan; Yip, Fuyuen; Nyagol, Ronald; Quick, Robert; Sage, Mike; Bruce, Nigel

2016-01-01

Household air pollution (HAP) from biomass fuel burning is linked to poor health outcomes. Improved biomass cookstoves (ICS) have the potential to improve HAP. A pre-/post- intervention study assessed the impact of six ICS on indoor air quality and acceptability of ICS to local users in rural Western Kenya. We measured mean personal and kitchen level concentrations of particulate matter <2.5μm in diameter (PM2.5, μg/m3) and carbon monoxide (CO, ppm) during the 48-hour period of each ICS use in 45 households. We compared these levels to those observed with traditional 3-stone fire (TSF) use. We assessed ICS acceptability through interviews and focus groups. We evaluated association of stove type, fuel use, and factors related to cooking practices with mean kitchen PM2.5 and CO using multivariable regression. Stove type, exclusive ICS use (vs. concurrent TSF use), and the amount of fuel used were independently associated with kitchen PM2.5 and CO levels. Reductions (95%CI) in mean PM2.5 compared to TSF, ranged by ICS from 11.9% (-2.8-24.5) to 42.3% (32.3-50.8). Reductions in kitchen CO compared to TSF, ranged by ICS from -5.8% (-21.9-8.2) to 34.5% (23.2-44.1). Mean kitchen PM2.5 ranged from 319μg/m3 to 518μg/m3 by ICS. Women thought ICS were easy to use, more efficient, produced less smoke, and cooked faster, compared to TSF. Women also reported limitations for each ICS. We documented reductions in HAP from ICS compared to TSF. The PM2.5 levels with ICS use were still considerably higher than WHO indoor air quality guidelines. Achieving maximal potential of ICS requires adherence to more exclusive use and addressing user reported ICS limitations.

Efficient CO2-Reducing Activity of NAD-Dependent Formate Dehydrogenase from Thiobacillus sp. KNK65MA for Formate Production from CO2 Gas

PubMed Central

Cho, Dae Haeng; Kim, Min Hoo; Lee, Sang Hyun; Jung, Kwang Deog; Kim, Yong Hwan

2014-01-01

NAD-dependent formate dehydrogenase (FDH) from Candida boidinii (CbFDH) has been widely used in various CO2-reduction systems but its practical applications are often impeded due to low CO2-reducing activity. In this study, we demonstrated superior CO2-reducing properties of FDH from Thiobacillus sp. KNK65MA (TsFDH) for production of formate from CO2 gas. To discover more efficient CO2-reducing FDHs than a reference enzyme, i.e. CbFDH, five FDHs were selected with biochemical properties and then, their CO2-reducing activities were evaluated. All FDHs including CbFDH showed better CO2-reducing activities at acidic pHs than at neutral pHs and four FDHs were more active than CbFDH in the CO2 reduction reaction. In particular, the FDH from Thiobacillus sp. KNK65MA (TsFDH) exhibited the highest CO2-reducing activity and had a dramatic preference for the reduction reaction, i.e., a 84.2-fold higher ratio of CO2 reduction to formate oxidation in catalytic efficiency (k cat/K B) compared to CbFDH. Formate was produced from CO2 gas using TsFDH and CbFDH, and TsFDH showed a 5.8-fold higher formate production rate than CbFDH. A sequence and structural comparison showed that FDHs with relatively high CO2-reducing activities had elongated N- and C-terminal loops. The experimental results demonstrate that TsFDH can be an alternative to CbFDH as a biocatalyst in CO2 reduction systems. PMID:25061666

Adaptive Engine Technologies for Aviation CO2 Emissions Reduction

NASA Technical Reports Server (NTRS)

Mercer, Carolyn R.; Haller, William J.; Tong, Michael T.

2006-01-01

Adaptive turbine engine technologies are assessed for their potential to reduce carbon dioxide emissions from commercial air transports.Technologies including inlet, fan, and compressor flow control, compressor stall control, blade clearance control, combustion control, active bearings and enabling technologies such as active materials and wireless sensors are discussed. The method of systems assessment is described, including strengths and weaknesses of the approach. Performance benefit estimates are presented for each technology, with a summary of potential emissions reduction possible from the development of new, adaptively controlled engine components.

Combining CO 2 reduction with propane oxidative dehydrogenation over bimetallic catalysts

DOE PAGES

Gomez, Elaine; Kattel, Shyam; Yan, Binhang; ...

2018-04-11

In this paper, the inherent variability and insufficiencies in the co-production of propylene from steam crackers has raised concerns regarding the global propylene production gap and has directed industry to develop more on-purpose propylene technologies. The oxidative dehydrogenation of propane by CO 2 (CO 2-ODHP) can potentially fill this gap while consuming a greenhouse gas. Non-precious FeNi and precious NiPt catalysts supported on CeO 2 have been identified as promising catalysts for CO 2-ODHP and dry reforming, respectively, in flow reactor studies conducted at 823 K. In-situ X-ray absorption spectroscopy measurements revealed the oxidation states of metals under reaction conditionsmore » and density functional theory calculations were utilized to identify the most favorable reaction pathways over the two types of catalysts.« less

Use of 13C Labeled Carbon Tetrachloride to Demonstrate the Transformation to Carbon Dioxide under Anaerobic Conditions in a Continuous Flow Column

NASA Astrophysics Data System (ADS)

Semprini, L.; Azizian, M.

2012-12-01

The demonstration of transformation of chlorinated aliphatic compounds (CAHs) in the subsurface is a challenge, especially when the products are carbon dioxide (CO2) and chloride ion. The groundwater contaminant carbon tetrachloride (CT) is of particular interest since a broad range of transformation products can be potentially formed under anaerobic conditions. The ability to demonstrate the transformation of CT to CO2 as a non toxic endproduct, is also of great interest. Results will be presented from a continuous flow column study where 13C labeled CT was used to demonstrate its transformation to CO2. The column was packed with a quartz sand and bioaugmented the Evanite Culture (EV) that is capable of transforming tetrachloroethene (PCE) to ethene. The column was continously fed a synthetic groundwater that was amended with PCE (0.10 mM) and either formate (1.5 mM) or lactate (1.1 mM), which ferments to produce hydrogen (H2) as the ultimate electron donor. Earlier CT transformation studies with the column, in the absence of sulfate reduction, and with formate added as a donor found CT (0.015 mM) was over 98% transformed with about 20% converted to chloroform (CF) (0.003 mM) and with a transient detection of chloromethane (CM). Methane and carbon disulfide, as potential products, were not detected. Neither CT nor CF inhibited the reductive dehalogenation of PCE to ethene. A series of transient studies conducted after these initial CT transformation tests, but in the absence of CT, showed formate remained an effective substrate for maintaining sulfate reduction and PCE transformation. Lactate, which was effectively fermented prior to CT addition, was not effectively fermented, with propionate accumulating as a fermentation product. When lactate was added, PCE was mainly transformed to cis-dichloroethene (cis-DCE) and VC, and sulfate reduction did not occur. In order to restore effective lactate fermentation the column was then bioaugmented with an EV culture that was capable of lactate fermentation. After bioaugmentation, effective lactate fermentation, sulfate reduction and PCE transformation to ethene was achieved. Unlabeled CT (0.015 mM) addition was then started and complete transformation was achieved with a transient build-up of CF and chloromethane, which were subsequently removed below their detection limits. CT continued to be completely transformed after the influent concentration was increased to 0.03 mM. 13C labeled CT (0.03 mM) was then added to the column. GC-MS analysis showed that 13C labeled CO2 was formed at near stoichiometric levels to the CT that was transformed. The results clearly demonstrate that CT can being transformed to CO2 at high CT concentrations, while maintaining effective PCE dehalogenation, sulfate reduction and lactate fermentation. The results also illustrate the great potential of using 13C labeled compounds in subsurface investigations.

Impact of naturally leaking carbon dioxide on soil properties and ecosystems in the Qinghai-Tibet plateau.

PubMed

Zhao, Xiaohong; Deng, Hongzhang; Wang, Wenke; Han, Feng; Li, Chunrong; Zhang, Hui; Dai, Zhenxue

2017-06-07

One of the major concerns for CO 2 capture and storage (CCS) is the potential risk of CO 2 leakage from storage reservoirs on the shallow soil property and vegetation. This study utilizes a naturally occurring CO 2 leaking site in the Qinghai-Tibet Plateau to analog a "leaking CCS site". Our observations from this site indicates that long-term CO 2 invasion in the vadose zone results in variations of soil properties, such as pH fluctuation, slight drop of total organic carbon, reduction of nitrogen and phosphorus, and concentration changes of soluble ions. Simultaneously, XRD patterns of the soil suggest that crystallization of soil is enhanced and mineral contents of calcite and anorthite in soil are increased substantially. Parts of the whole ecosystem such as natural wild plants, soil dwelling animals and microorganisms in shallow soil are affected as well. Under a moderate CO 2 concentration (less than 110000 ppm), wild plant growth and development are improved, while an intensive CO 2 flux over 112000 ppm causes adverse effects on the plant growth, physiological and biochemical system of plants, and crop quality of wheat. Results of this study provide valuable insight for understanding the possible environmental impacts associated with potential CO 2 leakage into shallow sediments at carbon sequestration sites.

Physiological importance of the heterodisulfide of coenzyme M and 7-mercaptoheptanoylthreonine phosphate in the reduction of carbon dioxide to methane in Methanobacterium

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

Bobik, T.A.; Wolfe, R.S.

1988-01-01

The heterodisulfide of the two coenzymes 2-mercaptoethanesulfonic acid (coenzyme M, HS-CoM) and N-(7-mercaptoheptanoyl)threonine O/sup 3/-phosphate (HS-HTP) increased the rate of CO/sub 2/ reduction to methane by cell extracts 42-fold. The stimulation resulted from activation of the initial step of methanogenesis, the production of formylmethanofuran from methanofuran and CO/sub 2/. These results establish a role for this heterodisulfide (CoM-S-S-HTP) in the reduction of CO/sub 2/ to formylmethanofuran. Evidence indicates that CoM-S-S-HTP is the labile intermediate that accounts for the coupling of the reduction of 2-(methylthio)ethanesulfonic acid by the methylreductase to formylmethanofuran biosynthesis, the RPG effect. The heterodisulfide was found to bemore » labile in cell extracts due to enzyme-catalyzed reduction and possibly thiol-disulfide exchange.« less

Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO 2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH 3 )] 2+ (6DHBP = 6,6'-(OH) 2 bpy)

DOE PAGES

Duan, Lele; Manbeck, Gerald F.; Kowalczyk, Marta; ...

2016-04-14

Ruthenium complexes with proton-responsive ligands [Ru(tpy)(nDHBP)(NCCH 3)](CF 3SO 3) 2 (tpy = 2,2':6',2"-terpyridine; nDHBP = n,n'-dihydroxy-2,2'-bipyridine, n = 4 or 6) were examined in this study for reductive chemistry and as catalysts for CO 2 reduction. Electrochemical reduction of [Ru(tpy)(nDHBP)(NCCH 3)] 2+ generates deprotonated species through interligand electron transfer in which the initially formed tpy radical anion reacts with a proton source to produce singly and doubly deprotonated complexes that are identical to those obtained by base titration. A third reduction (i.e., reduction of [Ru(tpy)(nDHBP–2H +)] 0) triggers catalysis of CO 2 reduction; however, the catalytic efficiency is strikingly lowermore » than that of unsubstituted [Ru(tpy)(bpy)(NCCH 3)] 2+ (bpy = 2,2'-bipyridine). Cyclic voltammetry, bulk electrolysis, and spectroelectrochemical infrared experiments suggest the reactivity of CO 2 at both the Ru center and the deprotonated quinone-type ligand. Lastly, the Ru carbonyl formed by the intermediacy of a metallocarboxylic acid is stable against reduction, and mass spectrometry analysis of this product indicates the presence of two carbonates formed by the reaction of DHBP–2H + with CO 2.« less

Mitigation of CO2 emissions from the EU-15 building stock: beyond the EU Directive on the Energy Performance of Buildings.

PubMed

Petersdorff, Carsten; Boermans, Thomas; Harnisch, Jochen

2006-09-01

GOAL SCOPE AND BACKGROUND: The European Directive on Energy Performance of Buildings which came into force 16 December 2002 will be implemented in the legislation of Member States by 4 January 2006. In addition to the aim of improving the overall energy efficiency of new buildings, large existing buildings will become a target for improvement, as soon as they undergo significant renovation. The building sector is responsible for about 40% of Europe's total end energy consumption and hence this Directive is an important step for the European Union in order that it should reach the level of saving required by the Kyoto Agreement. In this the EU is committed to reduce CO2 emissions relative to the base year of 1990 by 8 per cent, by 2010. But what will be the impact of the new Directive, how large could be the impacts of extending the obligation for energy efficiency retrofitting towards smaller buildings? Can improvement of the insulation offset or reduce the growing energy consumption from the increasing installation of cooling installations? EURIMA, the European Insulation Manufacturers Association and EuroACE, the European Alliance of Companies for Energy Efficiency in Buildings, asked Ecofys to address these questions. The effect of the EPB Directive on the emissions associated with the heating energy consumption of the total EU 15 building stock has been examined in a model calculation, using the Built Environment Analysis Model (BEAM), which was developed by Ecofys to investigate energy saving measures in the building stock. The great complexity of the EU-15 building stock had to be simplified by examining five standard buildings with eight insulation standards, which are assigned to building age and renovation status. Furthermore, three climatic regions (cold, moderate, warm) were distinguished for the calculation of the heating energy demand. This gave a basic 210 building types for which the heating energy demand and CO2 emissions from heating were calculated according to the principles of the European Norm EN 832. The model calculations demonstrates that the main contributor to the total heating related CO2 emissions of 725 Mt/a from the EU building stock in 2002 is the residential sector (77%) while the remaining 23% originates from non-residential buildings. In the residential sector, single-family houses represent the largest group responsible for 60% of the total CO2 emissions equivalent to 435 Mt/a. THE TECHNICAL POTENTIAL: If all retrofit measures in the scope of the Directive were realised immediately for the complete residential and non-residential building stock the overall CO2 emission savings would add up to 82 Mt/a. An additional saving potential compared to the Directive of 69 Mt/a would be created if the scope of the Directive was extended to cover retrofit measures in multi-family dwellings (200-1000 m2) and non-residential buildings smaller than 1000 m2 used floor space. In addition including the large group of single-family dwellings would lead to a potential for additional CO2 emission reductions compared to the Directive of 316 Mt/a. TEMPORAL MOBILIZATION OF THE POTENTIAL: Calculations based on the building stock as it develops over time with average retrofit rates demonstrated that regulations introduced following the EPB Directive result in a CO2 emissions decrease of 34 Mt/a by the year 2010 compared to the business as usual scenario. Extending the scope of the EPB Directive to all residential buildings (including single and multi-family dwellings), the CO2 emission savings potential over the 'business as usual' scenario could be doubled to 69 Mt/a in the year 2010. This creates an additional saving potential compared to the Directive of 36 Mt/a. COOLING DEMAND: The analysis demonstrated that in warm climatic zones the cooling demand can be reduced drastically by a combination of lowering the internal heat loads and by improved insulation. With the reduction of the heat loads to a moderate level the cooling demand, e.g. of a terraced house located in Madrid, can be reduced by an additional 85% if the insulation level is improved appropriately. This study demonstrates that the European Directive on Energy Performance of Buildings will have a significant impact on the CO2 emissions of the European building stock. The main saving potential lies in insulation of the existing building stock. Beyond this, CO2 emissions could, however, be greatly reduced if the scope of the Directive were to be extended to include retrofit of smaller buildings. The reductions should be seen in relation to the remaining gap of 190 Mt CO2 eq. per annum between the current emission levels of EU-15 and the target under the Kyoto-Protocol for the year 2010. The energy and industrial sector will probably contribute only a fraction of this reduction via the newly established EU emissions trading scheme and connected projects under the flexible mechanism. In addition, the traffic sector is likely to continue its growth path leading to a widening of the gap. Thus, there is likely to be considerable pressure on the EU building sector to contribute to the EU climate targets beyond what will be achieved by means of the current EPB Directive. Legislators on the EU and national level are therefore advised to take accelerated actions to tap the very significant emission reduction potentials available in the EU building stock.

Photoelectrocatalytic reduction of CO2 to methanol over a photosystem II-enhanced Cu foam/Si-nanowire system.

PubMed

Lian, Zichao; Pan, Donglai; Wang, Wenchao; Zhang, Dieqing; Li, Guisheng; Li, Hexing

2017-10-01

A solar-light double illumination photoelectrocatalytic cell (SLDIPEC) was fabricated for autonomous CO 2 reduction and O 2 evolution with the aid of photosystem II (PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires (Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO 2 conversion to methanol, with a high evolution rate (41.94mmol/hr), owing to fast electron transfer from PS-II to Cu foam. Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage (0.5V), and a suitable conduction band potential of Si (-0.6eV) allowed CO 2 to be easily reduced to CH 3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO 2 (8.03mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy. Copyright © 2017. Published by Elsevier B.V.

Controlled cobalt doping in biogenic magnetite nanoparticles

PubMed Central

Byrne, J. M.; Coker, V. S.; Moise, S.; Wincott, P. L.; Vaughan, D. J.; Tuna, F.; Arenholz, E.; van der Laan, G.; Pattrick, R. A. D.; Lloyd, J. R.; Telling, N. D.

2013-01-01

Cobalt-doped magnetite (CoxFe3 −xO4) nanoparticles have been produced through the microbial reduction of cobalt–iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites. PMID:23594814

Controlled cobalt doping in biogenic magnetite nanoparticles.

PubMed

Byrne, J M; Coker, V S; Moise, S; Wincott, P L; Vaughan, D J; Tuna, F; Arenholz, E; van der Laan, G; Pattrick, R A D; Lloyd, J R; Telling, N D

2013-06-06

Cobalt-doped magnetite (CoxFe3 -xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe(2+) site with Co(2+), with up to 17 per cent Co substituted into tetrahedral sites.

Indirect Z-Scheme BiOI/g-C3N4 Photocatalysts with Enhanced Photoreduction CO2 Activity under Visible Light Irradiation.

PubMed

Wang, Ji-Chao; Yao, Hong-Chang; Fan, Ze-Yu; Zhang, Lin; Wang, Jian-She; Zang, Shuang-Quan; Li, Zhong-Jun

2016-02-17

Rational design and construction of Z-scheme photocatalysts has received much attention in the field of CO2 reduction because of its great potential to solve the current energy and environmental crises. In this study, a series of Z-scheme BiOI/g-C3N4 photocatalysts are synthesized and their photocatalytic performance for CO2 reduction to produce CO, H2 and/or CH4 is evaluated under visible light irradiation (λ > 400 nm). The results show that the as-synthesized composites exhibit more highly efficient photocatalytic activity than pure g-C3N4 and BiOI and that the product yields change remarkably depending on the reaction conditions such as irradiation light wavelength. Emphasis is placed on identifying how the charge transfers across the heterojunctions and an indirect Z-scheme charge transfer mechanism is verified by detecting the intermediate I3(-) ions. The reaction mechanism is further proposed based on the detection of the intermediate (•)OH and H2O2. This work may be useful for rationally designing of new types of Z-scheme photocatalyst and provide some illuminating insights into the Z-scheme transfer mechanism.

Gram-Scale Synthesized Pd2Co-Supported PtMonolayers Electrocatalysts for Oxygen Reduction Reaction

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

Zhou, W.P.; Sasaki, K.; Su, D.

2010-04-21

Gram-scale synthesis of Pt{sub ML} electrocatalysts with a well-defined core-shell structure has been carried out using method involving galvanic displacement of an underpotential deposition Cu layer. The Pt shell thickness can be controlled by stepwise deposition. The Pt{at}Pd{sub 2}Co/C nanoparticles were characterized by X-ray powder diffraction, aberration-corrected scanning transmission electron microscopy, high-resolution energy-loss spectrometry, and in situ X-ray absorption spectroscopy. A complete Pt shell of 0.6 nm on a Pd{sub 2}Co core has been confirmed. The Pt{at}Pd{sub 2}Co/C core-shell electrocatalysts showed a very high activity for the oxygen reduction reaction; the Pt mass and specific activity were 0.72 A mg{supmore » -1}{sub Pt} and 0.5 mA cm{sup -2}, respectively (3.5 and 2.5 times higher than the corresponding values for commercial Pt catalysts), at 0.9 V in 0.1 M HClO{sub 4} at room temperature. In an accelerated potential cycling test, a loss in active surface area and a decrease in catalytic activity for gram-scale-synthesized Pt{sub ML} catalysts were also determined.« less

Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory.

PubMed

Fowler, Nicholas J; Blanford, Christopher F; Warwicker, Jim; de Visser, Sam P

2017-11-02

Blue copper proteins, such as azurin, show dramatic changes in Cu 2+ /Cu + reduction potential upon mutation over the full physiological range. Hence, they have important functions in electron transfer and oxidation chemistry and have applications in industrial biotechnology. The details of what determines these reduction potential changes upon mutation are still unclear. Moreover, it has been difficult to model and predict the reduction potential of azurin mutants and currently no unique procedure or workflow pattern exists. Furthermore, high-level computational methods can be accurate but are too time consuming for practical use. In this work, a novel approach for calculating reduction potentials of azurin mutants is shown, based on a combination of continuum electrostatics, density functional theory and empirical hydrophobicity factors. Our method accurately reproduces experimental reduction potential changes of 30 mutants with respect to wildtype within experimental error and highlights the factors contributing to the reduction potential change. Finally, reduction potentials are predicted for a series of 124 new mutants that have not yet been investigated experimentally. Several mutants are identified that are located well over 10 Å from the copper center that change the reduction potential by more than 85 mV. The work shows that secondary coordination sphere mutations mostly lead to long-range electrostatic changes and hence can be modeled accurately with continuum electrostatics. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Comparing the magnitude of simulated residential rebound effects from electric end-use efficiency across the US

NASA Astrophysics Data System (ADS)

Thomas, Brinda A.; Hausfather, Zeke; Azevedo, Inês L.

2014-07-01

Many US states rely on energy efficiency goals as a strategy to reduce CO2e emissions and air pollution, to minimize investments in new power plants, and to create jobs. For those energy efficiency interventions that are cost-effective, i.e., saving money and reducing energy, consumers may increase their use of energy services, or re-spend cost savings on other carbon- and energy-intensive goods and services. In this paper, we simulate the magnitude of these ‘rebound effects’ in each of the 50 states in terms of CO2e emissions, focusing on residential electric end-uses under plausible assumptions. We find that a 10% reduction in annual electricity use by a household results in an emissions’ reduction penalty ranging from 0.1 ton CO2e in California to 0.3 ton CO2e in Alabama (from potential emissions reductions of 0.3 ton CO2e and 1.6 ton CO2e, respectively, in the no rebound case). Rebound effects, percentage-wise, range from 6% in West Virginia (which has a high-carbon electricity and low electricity prices), to as high as 40% in California (which has low-carbon electricity and high electricity prices). The magnitude of rebound effects percentage-wise depends on the carbon intensity of the grid: in states with low emissions factors and higher electricity prices, such as California, the rebound effects are much larger percentage-wise than in states like Pennsylvania. Conversely, the states with larger per cent rebound effects are the ones where the implications in terms of absolute emissions changes are the smallest.

Biogeochemical modeling of CO 2 and CH 4 production in anoxic Arctic soil microcosms

DOE PAGES

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; ...

2016-09-12

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

The influence of food supply on the response of Olympia oyster larvae to ocean acidification

NASA Astrophysics Data System (ADS)

Hettinger, A.; Sanford, E.; Hill, T. M.; Hosfelt, J. D.; Russell, A. D.; Gaylord, B.

2013-10-01

Increases in atmospheric carbon dioxide drive accompanying changes in the marine carbonate system as carbon dioxide (CO2) enters seawater and alters ocean pH (termed "ocean acidification"). However, such changes do not occur in isolation, and other environmental factors have the potential to modulate the consequences of altered ocean chemistry. Given that physiological mechanisms used by organisms to confront acidification can be energetically costly, we explored the potential for food supply to influence the response of Olympia oyster (Ostrea lurida) larvae to ocean acidification. In laboratory experiments, we reared oyster larvae under a factorial combination of pCO2 and food level. Elevated pCO2 had negative effects on larval growth, total dry weight, and metamorphic success, but high food availability partially offset these influences. The combination of elevated pCO2 and low food availability led to the greatest reduction in larval performance. However, the effects of food and pCO2 interacted additively rather than synergistically, indicating that they operated independently. Despite the potential for abundant resources to counteract the consequences of ocean acidification, impacts were never completely negated, suggesting that even under conditions of enhanced primary production and elevated food availability, impacts of ocean acidification may still accrue in some consumers.

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.

Mechanism of photocatalytic reduction of CO 2 by Re(bpy)(CO) 3Cl from differences in carbon isotope discrimination

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

Schneider, Taylor W.; Ertem, Mehmed Z.; Muckerman, James T.

2016-08-01

The rhenium complex Re(bpy)(CO) 3Cl (1, bpy = 2,2'-bipyridine) catalyzes CO 2 reduction to CO in mixtures containing triethanolamine (TEOA) as a sacrificial reductant. The mechanism of this reaction under photocatalytic conditions remains to be fully characterized. Here, we report the competitive carbon kinetic isotope effects ( 13C KIEs) on photocatalytic CO 2 reduction by 1 and analyze the results of experimental measurements by comparing with computed KIEs via density functional theory (DFT) calculations as a means of formulating a chemical mechanism and illustrating the utility of this approach. The 13C KIEs, k( 12C)/k( 13C), in acetonitrile (ACN) and dimethylformamidemore » (DMF) were determined to be 1.0718 ± 0.0036 and 1.0685 ± 0.0075, respectively. When [Ru(bpy) 3]Cl 2 is added to the reaction mixture in acetonitrile as a photosensitizer, the reduction of CO 2 exhibited a 13C KIE = 1.0703 ± 0.0043. These values are consistent with the calculated isotope effect of CO 2 binding to the one-electron reduced [ReI(bpy• –)(CO) 3] species. The findings reported here provide strong evidence that the reactions in the two different solvents have the same first irreversible step and proceed with similar reactive intermediates upon reduction. Theoretically, we found that the major contribution for the large 13C isotope effects comes from a dominant zero-point energy (ZPE) term. Lastly, these results lay the groundwork for combined experimental and theoretical approaches for analysis of competitive isotope effects toward understanding CO 2 reduction catalyzed by other complexes.« less

Photo-reduction of CO2 Using a Rhenium Complex Covalently Supported on a Graphene/TiO2 Composite.

PubMed

Cui, Shi-Cong; Sun, Xue-Zhong; Liu, Jin-Gang

2016-07-07

One of the promising solutions for decreasing atmospheric CO2 is artificial photosynthesis, in which CO2 can be photoconverted into solar fuels. In this study, a rhenium complex Re(PyBn)(CO)3 Cl (PyBn=1-(2-picolyl)-4-phenyl-1H-1,2,3-triazole) was covalently grafted onto the surface of reduced graphene oxide (rGO). This was further combined with TiO2 to fabricate a novel catalyst composite TiO2 -rGO-Re(PyBn)(CO)3 Cl for CO2 photo-reduction. This hybrid composite demonstrated high selectivity conversion of CO2 into CO under xenon-lamp irradiation. Compared with the unsupported homogeneous catalyst Re(PyBn)(CO)3 Cl, the covalent immobilized catalyst composite TiO2 -rGO-Re(PyBn)(CO)3 Cl enhanced the turnover number six times and significantly improved catalyst stability. During the process of CO2 photo-reduction, intermediate species with lifetimes longer than hundreds of microseconds were observed and the formation of CO products was revealed using timeresolved infrared spectroscopy. A plausible mechanism for CO2 photo-reduction by the TiO2 -rGO-Re(PyBn)(CO)3 Cl catalyst composite has been suggested. The obtained results have implications for the future design of efficient catalyst composites for CO2 photo-conversion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Plasma Processing of Iron Ore

NASA Astrophysics Data System (ADS)

Sabat, Kali Charan; Murphy, Anthony B.

2017-06-01

Iron is currently produced by carbothermic reduction of oxide ores. This is a multiple-stage process that requires large-scale equipment and high capital investment, and produces large amounts of CO2. An alternative to carbothermic reduction is reduction using a hydrogen plasma, which comprises vibrationally excited molecular, atomic, and ionic states of hydrogen, all of which can reduce iron oxides, even at low temperatures. Besides the thermodynamic and kinetic advantages of a hydrogen plasma, the byproduct of the reaction is water, which does not pose any environmental problems. A review of the theory and practice of iron ore reduction using a hydrogen plasma is presented. The thermodynamic and kinetic aspects are considered, with molecular, atomic and ionic hydrogen considered separately. The importance of vibrationally excited hydrogen molecules in overcoming the activation energy barriers, and in transferring energy to the iron oxide, is emphasized. Both thermal and nonthermal plasmas are considered. The thermophysical properties of hydrogen and argon-hydrogen plasmas are discussed, and their influence on the constriction and flow in the of arc plasmas is considered. The published R&D on hydrogen plasma reduction of iron oxide is reviewed, with both the reduction of molten iron ore and in-flight reduction of iron ore particles being considered. Finally, the technical and economic feasibility of the process are discussed. It is shown that hydrogen plasma processing requires less energy than carbothermic reduction, mainly because pelletization, sintering, and cokemaking are not required. Moreover, the formation of the greenhouse gas CO2 as a byproduct is avoided. In-flight reduction has the potential for a throughput at least equivalent to the blast furnace process. It is concluded that hydrogen plasma reduction of iron ore is a potentially attractive alternative to standard methods.

Reduction of Bromate by Cobalt-Impregnated Biochar Fabricated via Pyrolysis of Lignin Using CO2 as a Reaction Medium.

PubMed

Cho, Dong-Wan; Kwon, Gihoon; Ok, Yong Sik; Kwon, Eilhann E; Song, Hocheol

2017-04-19

In this study, pyrolysis of lignin impregnated with cobalt (Co) was conducted to fabricate a Co-biochar (i.e., Co/lignin biochar) for use as a catalyst for bromate (BrO 3 - ) reduction. Carbon dioxide (CO 2 ) was employed as a reaction medium in the pyrolysis to induce desired effects associated with CO 2 ; (1) the enhanced thermal cracking of volatile organic compounds (VOCs) evolved from the thermal degradation of biomass, and (2) the direct reaction between CO 2 and VOCs, which resulted in the enhanced generation of syngas (i.e., H 2 and CO). This study placed main emphases on three parts: (1) the role of impregnated Co in pyrolysis of lignin in the presence of CO 2 , (2) the characterization of Co/lignin biochar, and (3) evaluation of catalytic capability of Co-lignin biochar in BrO 3 - reduction. The findings from the pyrolysis experiments strongly evidenced that the desired CO 2 effects were strengthened due to catalytic effect of impregnated Co in lignin. For example, the enhanced generation of syngas from pyrolysis of Coimpregnated lignin in CO 2 was more significant than the case without Co impregnation. Moreover, pyrolysis of Coimpregnated lignin in CO 2 led to production of biochar of which surface area (599 m 2 g -1 ) is nearly 100 times greater than the biochar produced in N 2 (6.6 m 2 g -1 ). Co/lignin biochar produced in CO 2 also showed a great performance in catalyzing BrO 3 - reduction as compared to the biochar produced in N 2 .

Immobilization of cobalt by sulfate-reducing bacteria in subsurface sediments

USGS Publications Warehouse

Krumholz, Lee R.; Elias, Dwayne A.; Suflita, Joseph M.

2003-01-01

We investigated the impact of sulfate-reduction on immobilization of metals in subsurface aquifers. Co 2+ was used as a model for heavy metals. Factors limiting sulfate-reduction dependent Co 2+ immobilization were tested on pure cultures of sulfate-reducing bacteria, and in sediment columns from a landfill leachate contaminated aquifer. In the presence of 1 mM Co 2+ , the growth of pure cultures of sulfate-reducing bacteria was not impacted. Cultures of Desulfovibrio desulfuricans, Desulfotomaculum gibsoniae , and Desulfomicrobium hypogeia removed greater than 99.99% of the soluble Co 2+ when CoCl 2 was used with no chelators. The above cultures and Desulfoarcula baarsi removed 98-99.94% of the soluble Co(II) when the metal was complexed with the model ligand nitrilotriacetate (Co-NTA). Factors controlling the rate of sulfate-reduction based Co 2+ precipitation were investigated in sediment-cobalt mixtures. Several electron donors were tested and all but toluene accelerated soluble Co 2+ loss. Ethanol and formate showed the greatest stimulation. All complex nitrogen sources tested slowed and decreased the extent of Co 2+ removal from solution relative to formate-amended sediment incubations. A range of pH values were tested (6.35-7.81), with the more alkaline incubations exhibiting the largest precipitation of Co 2+ . The immobilization of Co 2+ in sediments was also investigated with cores to monitor the flow of Co 2+ through undisturbed sediments. An increase in the amount of Co 2+ immobilized as CoS was observed as sulfate reduction activity was stimulated in flow through columns. Both pure culture and sediment incubation data indicate that stimulation of sulfate reduction is a viable strategy in the immobilization of contaminating metals in subsurface systems.

Potential for reducing air pollution from oil refineries.

PubMed

Karbassi, A R; Abbasspour, M; Sekhavatjou, M S; Ziviyar, F; Saeedi, M

2008-10-01

Islamic Republic of Iran has to invest 95 billion US$ for her new oil refineries to the year 2045. At present, the emission factors for CO(2), NO( x ) and SO(2) are 3.5, 4.2 and 119 times higher than British refineries, respectively. In order to have a sustainable development in Iranian oil refineries, the government has to set emission factors of European Community as her goal. At present CO(2) per Gross Domestic Production (GDP) in the country is about 2.7 kg CO(2) as 1995's USD value that should be reduced to 1.25 kg CO(2)/GDP in the year 2015. Total capital investment for such reduction is estimated at 346 million USD which is equal to 23 USD/ton of CO(2). It is evident that mitigation of funds set by Clean Development Mechanism (3 to 7 USD/tons of CO(2)) is well below the actual capital investment needs. Present survey shows that energy efficiency promotion potential in all nine Iranian oil refineries is about 165,677 MWh/year through utilization of more efficient pumps and compressors. Better management of boilers in all nine refineries will lead to a saving of 273 million m(3) of natural gas per year.

Assessment of Clmate Change Mitigation Strategies for the Road Transport Sector of India

NASA Astrophysics Data System (ADS)

Singh, N.; Mishra, T.; Banerjee, R.

2017-12-01

India is one of the fastest growing major economies of the world. It imports three quarters of its oil demand, making transport sector major contributor of greenhouse gas (GHG) emissions. 40% of oil consumption in India comes from transport sector and over 90% of energy demand is from road transport sector. This has led to serious increase in CO2 emission and concentration of air pollutants in India. According to Intergovernmental Panel on Climate Change (IPCC), transport can play a crucial role for mitigation of global greenhouse gas emissions. Therefore, assessment of appropriate mitigation policies is required for emission reduction and cost benefit potential. The present study aims to estimate CO2, SO2, PM and NOx emissions from the road transport sector for the base year (2014) and target year (2030) by applying bottom up emission inventory model. Effectiveness of different mitigation strategies like inclusion of natural gas as alternate fuel, penetration of electric vehicle as alternate vehicle, improvement of fuel efficiency and increase share of public transport is evaluated for the target year. Emission reduction achieved from each mitigation strategies in the target year (2030) is compared with the business as usual scenario for the same year. To obtain cost benefit analysis, marginal abatement cost for each mitigation strategy is estimated. The study evaluates mitigation strategies not only on the basis of emission reduction potential but also on their cost saving potential.

Light induced changes of internal pH in a barnacle photoreceptor and the effect of internal pH on the receptor potential.

PubMed Central

Brown, H M; Meech, R W

1979-01-01

1. Intracellular pH (pH1) was measured in Balanus photoreceptors using pH-sensitive glass micro-electrodes. The average pH1 of twelve photoreceptors which had been dark adapted for at least 30 min was 7.3 +/- 0.07 (S.D.). 2. Illumination reduced the recorded pH1 by as much as 0.2 pH unit. The change in pH1 was graded with light intensity. 3. When the cells were exposed to CO2 in the dark, pH1 declined monophasically. Saline equilibrated with 2% CO2; 98% O2 produced a steady reduction in pH1 of about 0.25 unit in 2--3 min. The buffering capacity of the receptor cell cytoplasm calculated from such experiments is approximately 15 slykes. 4. In the presence of HCO3-1, CO2 saline produced smaller, biphasic changes in pH1. 5. The membrane depolarization produced by a bright flash (depolarizing receptor potential) was reversibly reduced in the presence of external CO2 or by injection of H+. Iontophoretic injection of HCO2- increased the amplitude of the receptor potential. 6. In individual cells there was a close correlation between the amplitude of the receptor potential and pH1. 7. Saline equilibrated with CO2 reduced the light induced current (recorded under voltage-clamp) by 40--50% without affecting its reversal potential. 8. Exposure of the receptor to 95% CO2 saline for several minutes (pH0 5.5) not only abolished the receptor potential but also reversibly decreased the K conductance of the membrane in the dark. These effects were not reproduced by pH0 5.5 buffered saline or by a 5 min exposure to saline equilibrated with N2. 9. It is suggested that changes in pH1 induced by light modulate the sensitivity of the receptor under physiological conditions. PMID:43890

Heterologous Expression of the Clostridium carboxidivorans CO Dehydrogenase Alone or Together with the Acetyl Coenzyme A Synthase Enables both Reduction of CO2 and Oxidation of CO by Clostridium acetobutylicum

PubMed Central

Carlson, Ellinor D.

2017-01-01

ABSTRACT With recent advances in synthetic biology, CO2 could be utilized as a carbon feedstock by native or engineered organisms, assuming the availability of electrons. Two key enzymes used in autotrophic CO2 fixation are the CO dehydrogenase (CODH) and acetyl coenzyme A (acetyl-CoA) synthase (ACS), which form a bifunctional heterotetrameric complex. The CODH/ACS complex can reversibly catalyze CO2 to CO, effectively enabling a biological water-gas shift reaction at ambient temperatures and pressures. The CODH/ACS complex is part of the Wood-Ljungdahl pathway (WLP) used by acetogens to fix CO2, and it has been well characterized in native hosts. So far, only a few recombinant CODH/ACS complexes have been expressed in heterologous hosts, none of which demonstrated in vivo CO2 reduction. Here, functional expression of the Clostridium carboxidivorans CODH/ACS complex is demonstrated in the solventogen Clostridium acetobutylicum, which was engineered to express CODH alone or together with the ACS. Both strains exhibited CO2 reduction and CO oxidation activities. The CODH reactions were interrogated using isotopic labeling, thus verifying that CO was a direct product of CO2 reduction, and vice versa. CODH apparently uses a native C. acetobutylicum ferredoxin as an electron carrier for CO2 reduction. Heterologous CODH activity depended on actively growing cells and required the addition of nickel, which is inserted into CODH without the need to express the native Ni insertase protein. Increasing CO concentrations in the gas phase inhibited CODH activity and altered the metabolite profile of the CODH-expressing cells. This work provides the foundation for engineering a complete and functional WLP in nonnative host organisms. IMPORTANCE Functional expression of CO dehydrogenase (CODH) from Clostridium carboxidivorans was demonstrated in C. acetobutylicum, which is natively incapable of CO2 fixation. The expression of CODH, alone or together with the C. carboxidivorans acetyl-CoA synthase (ACS), enabled C. acetobutylicum to catalyze both CO2 reduction and CO oxidation. Importantly, CODH exhibited activity in both the presence and absence of ACS. 13C-tracer studies confirmed that the engineered C. acetobutylicum strains can reduce CO2 to CO and oxidize CO during growth on glucose. PMID:28625981

Heterologous Expression of the Clostridium carboxidivorans CO Dehydrogenase Alone or Together with the Acetyl Coenzyme A Synthase Enables both Reduction of CO2 and Oxidation of CO by Clostridium acetobutylicum.

PubMed

Carlson, Ellinor D; Papoutsakis, Eleftherios T

2017-08-15

With recent advances in synthetic biology, CO 2 could be utilized as a carbon feedstock by native or engineered organisms, assuming the availability of electrons. Two key enzymes used in autotrophic CO 2 fixation are the CO dehydrogenase (CODH) and acetyl coenzyme A (acetyl-CoA) synthase (ACS), which form a bifunctional heterotetrameric complex. The CODH/ACS complex can reversibly catalyze CO 2 to CO, effectively enabling a biological water-gas shift reaction at ambient temperatures and pressures. The CODH/ACS complex is part of the Wood-Ljungdahl pathway (WLP) used by acetogens to fix CO 2 , and it has been well characterized in native hosts. So far, only a few recombinant CODH/ACS complexes have been expressed in heterologous hosts, none of which demonstrated in vivo CO 2 reduction. Here, functional expression of the Clostridium carboxidivorans CODH/ACS complex is demonstrated in the solventogen Clostridium acetobutylicum , which was engineered to express CODH alone or together with the ACS. Both strains exhibited CO 2 reduction and CO oxidation activities. The CODH reactions were interrogated using isotopic labeling, thus verifying that CO was a direct product of CO 2 reduction, and vice versa. CODH apparently uses a native C. acetobutylicum ferredoxin as an electron carrier for CO 2 reduction. Heterologous CODH activity depended on actively growing cells and required the addition of nickel, which is inserted into CODH without the need to express the native Ni insertase protein. Increasing CO concentrations in the gas phase inhibited CODH activity and altered the metabolite profile of the CODH-expressing cells. This work provides the foundation for engineering a complete and functional WLP in nonnative host organisms. IMPORTANCE Functional expression of CO dehydrogenase (CODH) from Clostridium carboxidivorans was demonstrated in C. acetobutylicum , which is natively incapable of CO 2 fixation. The expression of CODH, alone or together with the C. carboxidivorans acetyl-CoA synthase (ACS), enabled C. acetobutylicum to catalyze both CO 2 reduction and CO oxidation. Importantly, CODH exhibited activity in both the presence and absence of ACS. 13 C-tracer studies confirmed that the engineered C. acetobutylicum strains can reduce CO 2 to CO and oxidize CO during growth on glucose. Copyright © 2017 American Society for Microbiology.

Nickel containing CO dehydrogenases and hydrogenases.

PubMed

Ragsdale, S W

2000-01-01

The two redox catalysts described here can generate very low potential electrons in one direction and perform chemically difficult reductions in the other. The chemical transformations occur at unusual metal clusters. Spectroscopic, crystallographic, and kinetic analyses are converging on answers to how the metals in these clusters are arranged and how they are involved in the chemical and redox steps. The first structure of CO dehydrogenase, which will appear in the next year, will help define a firm chemical basis for future mechanistic studies. In the immediate future, we hope to learn whether the hydride intermediate in hydrogenase or the carbonyl intermediate in CO dehydrogenase bind to the Ni or Fe subsites in these heterometallic clusters. Or perhaps could they be bridged to two metals? Inter- and intramolecular wires have been proposed that connect the catalytic redox machine to proximal redox centers leading eventually to the ultimate redox partners. Elucidating the pathways of electron flow is a priority for the future. There is evidence for molecular channels delivering substrates to the active sites of these enzymes. In the next few years, these channels will be better defined. The products of CO2 and proton reduction are passed to the active sites of other enzymes and, in the case of H2, even passed from one organism to another. In the future, the mechanism of gas transfer will be uncovered. General principles of how these redox reactions are catalyzed are becoming lucid as the reactions are modeled theoretically and experimentally. Proton and CO2 reduction and the generation of C-C bonds from simple precursors are important reactions in industry. H2 could be the clean fuel of the future. Hopefully, the knowledge gained from studies of hydrogenase, CO dehydrogenase, and acetyl-CoA synthase can be used to improve life on earth.

Subsurface watering resulted in reduced soil N2O and CO2 emissions and their global warming potentials than surface watering

NASA Astrophysics Data System (ADS)

Wei, Qi; Xu, Junzeng; Yang, Shihong; Liao, Linxian; Jin, Guangqiu; Li, Yawei; Hameed, Fazli

2018-01-01

Water management is an important practice with significant effect on greenhouse gases (GHG) emission from soils. Nitrous oxide (N2O) and carbon dioxide (CO2) emissions and their global warming potentials (GWPs) from subsurface watering soil (SUW) were investigated, with surface watering (SW) as a control. Results indicated that the N2O and CO2 emissions from SUW soils were somewhat different to those from SW soil, with the peak N2O and CO2 fluxes from SUW soil reduced by 28.9% and 19.4%, and appeared 72 h and 168 h later compared with SW. The fluxes of N2O and CO2 from SUW soils were lower than those from SW soil in both pulse and post-pulse periods, and the reduction was significantly (p<0.05) in pulse period. Compare to SW, the cumulative N2O and CO2 emissions and its integrative GWPs from SUW soil decreased by 21.0% (p<0.05), 15.9% and 18.0%, respectively. The contributions of N2O to GWPs were lower than those of CO2 during most of time, except in pulse emission periods, and the proportion of N2O from SUW soil was 1.4% (p>0.1) lower that from SW soil. Moreover, N2O and CO2 fluxes from both watering treatments increased exponentially with increase of soil water-filled pore space (WFPS) and temperature. Our results suggest that watering soil from subsurface could significantly reduce the integrative greenhouse effect caused by N2O and CO2 and is a promising strategy for soil greenhouse gases (GHGs) mitigation. And the pulse period, contributed most to the reduction in emissions of N2O and CO2 from soils between SW and SUW, should be a key period for mitigating GHGs emissions. Response of N2O and CO2 emissions to soil WFPS and temperature illustrated that moisture was the dominant parameters that triggering GHG pulse emissions (especially for N2O), and temperature had a greater effect on the soil microorganism activity than moisture in drier soil. Avoiding moisture and temperature are appropriate for GHG emission at the same time is essential for GHGs mitigation, because peak N2O and CO2 emission were observed only when moisture and temperature are both appropriate.

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Understanding the differences between the wear of metal-on-metal and ceramic-on-metal total hip replacements.

PubMed

Figueiredo-Pina, C G; Yan, Y; Neville, A; Fisher, J

2008-04-01

Hip simulator studies have been carried out extensively to understand and test artificial hip implants in vitro as an efficient alternative to obtaining long-term results in vivo. Recent studies have shown that a ceramic-on-metal material combination lowers the wear by up to 100 times in comparison with a typical metal-on-metal design. The reason for this reduction remains unclear and for this reason this study has undertaken simple tribometer tests to understand the fundamental material loss mechanisms in two material combinations: metal-on-metal and ceramic-on-ceramic. A simple-configuration reciprocating pin-on-plate wear study was performed under open-circuit potential (OCP) and with applied cathodic protection (CP) in a serum solution using two tribological couples: firstly, cobalt-chromium (Co-Cr) pins against Co-Cr plates; secondly, Co-Cr pins against alumina (Al2O3) plates. The pin and plate surfaces prior to and after testing were examined by profilometry and scanning electron microscopy. The results showed a marked reduction in wear when CP was applied, indicating that total material degradation under the OCP condition was attributed to corrosion processes. The substitution of the Co-Cr pin with an Al2O3 plate also resulted in a dramatic reduction in wear, probably due to the reduction in the corrosion-wear interactions between the tribological pair.

Effects of CO2-induced pH reduction on the exoskeleton structure and biophotonic properties of the shrimp Lysmata californica

PubMed Central

Taylor, Jennifer R. A.; Gilleard, Jasmine M.; Allen, Michael C.; Deheyn, Dimitri D.

2015-01-01

The anticipated effects of CO2-induced ocean acidification on marine calcifiers are generally negative, and include dissolution of calcified elements and reduced calcification rates. Such negative effects are not typical of crustaceans for which comparatively little ocean acidification research has been conducted. Crustaceans, however, depend on their calcified exoskeleton for many critical functions. Here, we conducted a short-term study on a common caridean shrimp, Lysmata californica, to determine the effect of CO2-driven reduction in seawater pH on exoskeleton growth, structure, and mineralization and animal cryptic coloration. Shrimp exposed to ambient (7.99 ± 0.04) and reduced pH (7.53 ± 0.06) for 21 days showed no differences in exoskeleton growth (percent increase in carapace length), but the calcium weight percent of their cuticle increased significantly in reduced pH conditions, resulting in a greater Ca:Mg ratio. Cuticle thickness did not change, indicating an increase in the mineral to matrix ratio, which may have mechanical consequences for exoskeleton function. Furthermore, there was a 5-fold decrease in animal transparency, but no change in overall shrimp coloration (red). These results suggest that even short-term exposure to CO2-induced pH reduction can significantly affect exoskeleton mineralization and shrimp biophotonics, with potential impacts on crypsis, physical defense, and predator avoidance. PMID:26030212

Effects of CO2-induced pH reduction on the exoskeleton structure and biophotonic properties of the shrimp Lysmata californica.

PubMed

Taylor, Jennifer R A; Gilleard, Jasmine M; Allen, Michael C; Deheyn, Dimitri D

2015-06-01

The anticipated effects of CO2-induced ocean acidification on marine calcifiers are generally negative, and include dissolution of calcified elements and reduced calcification rates. Such negative effects are not typical of crustaceans for which comparatively little ocean acidification research has been conducted. Crustaceans, however, depend on their calcified exoskeleton for many critical functions. Here, we conducted a short-term study on a common caridean shrimp, Lysmata californica, to determine the effect of CO2-driven reduction in seawater pH on exoskeleton growth, structure, and mineralization and animal cryptic coloration. Shrimp exposed to ambient (7.99 ± 0.04) and reduced pH (7.53 ± 0.06) for 21 days showed no differences in exoskeleton growth (percent increase in carapace length), but the calcium weight percent of their cuticle increased significantly in reduced pH conditions, resulting in a greater Ca:Mg ratio. Cuticle thickness did not change, indicating an increase in the mineral to matrix ratio, which may have mechanical consequences for exoskeleton function. Furthermore, there was a 5-fold decrease in animal transparency, but no change in overall shrimp coloration (red). These results suggest that even short-term exposure to CO2-induced pH reduction can significantly affect exoskeleton mineralization and shrimp biophotonics, with potential impacts on crypsis, physical defense, and predator avoidance.

Predicting the Response of Molluscs to the Impact of Ocean Acidification

PubMed Central

Parker, Laura M.; Ross, Pauline M.; O’Connor, Wayne A.; Pörtner, Hans O.; Scanes, Elliot; Wright, John M.

2013-01-01

Elevations in atmospheric carbon dioxide (CO2) are anticipated to acidify oceans because of fundamental changes in ocean chemistry created by CO2 absorption from the atmosphere. Over the next century, these elevated concentrations of atmospheric CO2 are expected to result in a reduction of the surface ocean waters from 8.1 to 7.7 units as well as a reduction in carbonate ion (CO32−) concentration. The potential impact that this change in ocean chemistry will have on marine and estuarine organisms and ecosystems is a growing concern for scientists worldwide. While species-specific responses to ocean acidification are widespread across a number of marine taxa, molluscs are one animal phylum with many species which are particularly vulnerable across a number of life-history stages. Molluscs make up the second largest animal phylum on earth with 30,000 species and are a major producer of CaCO3. Molluscs also provide essential ecosystem services including habitat structure and food for benthic organisms (i.e., mussel and oyster beds), purification of water through filtration and are economically valuable. Even sub lethal impacts on molluscs due to climate changed oceans will have serious consequences for global protein sources and marine ecosystems. PMID:24832802

Ocean acidification and fertilization in the antarctic sea urchin Sterechinus neumayeri: the importance of polyspermy.

PubMed

Sewell, Mary A; Millar, Russell B; Yu, Pauline C; Kapsenberg, Lydia; Hofmann, Gretchen E

2014-01-01

Ocean acidification (OA), the reduction of the seawater pH as a result of increasing levels of atmospheric CO2, is an important climate change stressor in the Southern Ocean and Antarctic. We examined the impact of OA on fertilization success in the Antarctic sea urchin Sterechinus neumayeri using pH treatment conditions reflective of the current and near-future "pH seascape" for this species: current (control: pH 8.052, 384.1 μatm of pCO2), a high CO2 treatment approximating the 0.2-0.3 unit decrease in pH predicted for 2100 (high CO2: pH 7.830, 666.0 μatm of pCO2), and an intermediate medium CO2 (pH 7.967, 473.4 μatm of pCO2). Using a fertilization kinetics approach and mixed-effect models, we observed significant variation in the OA response between individual male/female pairs (N = 7) and a significant population-level increase (70-100%) in tb (time for a complete block to polyspermy) at medium and high CO2, a mechanism that potentially explains the higher levels of abnormal development seen in OA conditions. However, two pairs showed higher fertilization success with CO2 treatment and a nonsignificant effect. Future studies should focus on the mechanisms and levels of interindividual variability in OA response, so that we can consider the potential for selection and adaptation of organisms to a future ocean.

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

Komiyama, Ryoichi; Marnay, Chris; Stadler, Michael

In this analysis, the authors projected Japan's energy demand/supply and energy-related CO{sub 2} emissions to 2050. Their analysis of various scenarios indicated that Japan's CO{sub 2} emissions in 2050 could be potentially reduced by 26-58% from the current level (FY 2005). These results suggest that Japan could set a CO{sub 2} emission reduction target for 2050 at between 30% and 60%. In order to reduce CO{sub 2} emissions by 60% in 2050 from the present level, Japan will have to strongly promote energy conservation at the same pace as an annual rate of 1.9% after the oil crises (to cutmore » primary energy demand per GDP (TPES/GDP) in 2050 by 60% from 2005) and expand the share of non-fossil energy sources in total primary energy supply in 2050 to 50% (to reduce CO{sub 2} emissions per primary energy demand (CO{sub 2}/TPES) in 2050 by 40% from 2005). Concerning power generation mix in 2050, nuclear power will account for 60%, solar and other renewable energy sources for 20%, hydro power for 10% and fossil-fired generation for 10%, indicating substantial shift away from fossil fuel in electric power supply. Among the mitigation measures in the case of reducing CO{sub 2} emissions by 60% in 2050, energy conservation will make the greatest contribution to the emission reduction, being followed by solar power, nuclear power and other renewable energy sources. In order to realize this massive CO{sub 2} abatement, however, Japan will have to overcome technological and economic challenges including the large-scale deployment of nuclear power and renewable technologies.« less

Costs of mitigating CO2 emissions from passenger aircraft

NASA Astrophysics Data System (ADS)

Schäfer, Andreas W.; Evans, Antony D.; Reynolds, Tom G.; Dray, Lynnette

2016-04-01

In response to strong growth in air transportation CO2 emissions, governments and industry began to explore and implement mitigation measures and targets in the early 2000s. However, in the absence of rigorous analyses assessing the costs for mitigating CO2 emissions, these policies could be economically wasteful. Here we identify the cost-effectiveness of CO2 emission reductions from narrow-body aircraft, the workhorse of passenger air transportation. We find that in the US, a combination of fuel burn reduction strategies could reduce the 2012 level of life cycle CO2 emissions per passenger kilometre by around 2% per year to mid-century. These intensity reductions would occur at zero marginal costs for oil prices between US$50-100 per barrel. Even larger reductions are possible, but could impose extra costs and require the adoption of biomass-based synthetic fuels. The extent to which these intensity reductions will translate into absolute emissions reductions will depend on fleet growth.

Greenhouse Gas Mitigation Options in ISEEM Global Energy Model: 2010-2050 Scenario Analysis for Least-Cost Carbon Reduction in Iron and Steel Sector

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

Karali, Nihan; Xu, Tengfang; Sathaye, Jayant

The goal of the modeling work carried out in this project was to quantify long-term scenarios for the future emission reduction potentials in the iron and steel sector. The main focus of the project is to examine the impacts of carbon reduction options in the U.S. iron and steel sector under a set of selected scenarios. In order to advance the understanding of carbon emission reduction potential on the national and global scales, and to evaluate the regional impacts of potential U.S. mitigation strategies (e.g., commodity and carbon trading), we also included and examined the carbon reduction scenarios in China’smore » and India’s iron and steel sectors in this project. For this purpose, a new bottom-up energy modeling framework, the Industrial Sector Energy Efficiency Modeling (ISEEM), (Karali et al. 2012) was used to provide detailed annual projections starting from 2010 through 2050. We used the ISEEM modeling framework to carry out detailed analysis, on a country-by-country basis, for the U.S., China’s, and India’s iron and steel sectors. The ISEEM model applicable to iron and steel section, called ISEEM-IS, is developed to estimate and evaluate carbon emissions scenarios under several alternative mitigation options - including policies (e.g., carbon caps), commodity trading, and carbon trading. The projections will help us to better understand emission reduction potentials with technological and economic implications. The database for input of ISEEM-IS model consists of data and information compiled from various resources such as World Steel Association (WSA), the U.S. Geological Survey (USGS), China Steel Year Books, India Bureau of Mines (IBM), Energy Information Administration (EIA), and recent LBNL studies on bottom-up techno-economic analysis of energy efficiency measures in the iron and steel sector of the U.S., China, and India, including long-term steel production in China. In the ISEEM-IS model, production technology and manufacturing details are represented, in addition to the extensive data compiled from recent studies on bottom-up representation of efficiency measures for the sector. We also defined various mitigation scenarios including long-term production trends to project country-specific production, energy use, trading, carbon emissions, and costs of mitigation. Such analyses can provide useful information to assist policy-makers when considering and shaping future emissions mitigation strategies and policies. The technical objective is to analyze the costs of production and CO 2 emission reduction in the U.S, China, and India’s iron and steel sectors under different emission reduction scenarios, using the ISEEM-IS as a cost optimization model. The scenarios included in this project correspond to various CO 2 emission reduction targets for the iron and steel sector under different strategies such as simple CO 2 emission caps (e.g., specific reduction goals), emission reduction via commodity trading, and emission reduction via carbon trading.« less

Energy-Efficiency and Air-Pollutant Emissions-Reduction Opportunities for the Ammonia Industry in China

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

Ma, Ding; Hasanbeigi, Ali; Chen, Wenying

As one of the most energy-intensive and polluting industries, ammonia production is responsible for significant carbon dioxide (CO 2) and air-pollutant emissions. Although many energy-efficiency measures have been proposed by the Chinese government to mitigate greenhouse gas emissions and improve air quality, lack of understanding of the cost-effectiveness of such improvements has been a barrier to implementing these measures. Assessing the costs, benefits, and cost-effectiveness of different energy-efficiency measures is essential to advancing this understanding. In this study, a bottom-up energy conservation supply curve model is developed to estimate the potential for energy savings and emissions reductions from 26 energy-efficiencymore » measures that could be applied in China’s ammonia industry. Cost-effective implementation of these measures saves a potential 271.5 petajoules/year for fuel and 5,443 gigawatt-hours/year for electricity, equal to 14% of fuel and 14% of electricity consumed in China’s ammonia industry in 2012. These reductions could mitigate 26.7 million tonnes of CO 2 emissions. This study also quantifies the co-benefits of reducing air-pollutant emissions and water use that would result from saving energy in China’s ammonia industry. This quantitative analysis advances our understanding of the cost-effectiveness of energy-efficiency measures and can be used to augment efforts to reduce energy use and environmental impacts.« less

Anaerobic oxidation of [1,2-14C]Dichloroethene under Mn(IV)-reducing conditions

USGS Publications Warehouse

Bradley, Paul M.; Landmeyer, James E.; Dinicola, Richard S.

1998-01-01

Anaerobic oxidation of [1,2-14C]dichloroethene to14CO2 under Mn(IV)-reducing conditions was demonstrated. The results indicate that oxidative degradation of partially chlorinated solvents like dichloroethene can be significant even under anoxic conditions and demonstrate the potential importance of Mn(IV) reduction for remediation of chlorinated groundwater contaminants.

Catholyte-Free Electrocatalytic CO2 Reduction to Formate.

PubMed

Lee, Wonhee; Kim, Young Eun; Youn, Min Hye; Jeong, Soon Kwan; Park, Ki Tae

2018-04-16

Electrochemical reduction of carbon dioxide (CO 2 ) into value-added chemicals is a promising strategy to reduce CO 2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO 2 reduction (CO 2 R) is the low solubility of CO 2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte-free electrocatalytic CO 2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm -2 , despite the decrease in CO 2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L -1 is obtained as a one-path product at 343 K with high PCD (51.7 mA cm -2 ) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrolysis Treatment of Chromite Ore Processing Residue by Biomass: Cellulose Pyrolysis and Cr(VI) Reduction Behavior.

PubMed

Zhang, Da-Lei; Zhang, Mei-Yi; Zhang, Chu-Hui; Sun, Ying-Jie; Sun, Xiao; Yuan, Xian-Zheng

2016-03-15

The pyrolysis treatment with biomass is a promising technology for the remediation of chromite-ore-processing residue (COPR). However, the mechanism of this process is still unclear. In this study, the behavior of pyrolysis reduction of Cr(VI) by cellulose, the main component of biomass, was elucidated. The results showed that the volatile fraction (VF) of cellulose, ie. gas and tar, was responsible for Cr(VI) reduction. All organic compounds, as well as CO and H2 in VF, potentially reduced Cr(VI). X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine-structure (EXAFS) spectroscopy confirmed the reduction of Cr(VI) to Cr(III) and the formation of amorphous Cr2O3. The remnant Cr(VI) content in COPR can be reduced below the detection limit (2 mg/kg) by the reduction of COPR particle and extension of reaction time between VF and COPR. This study provided a deep insight on the co-pyrolysis of cellulose with Cr(VI) in COPR and an ideal approach by which to characterize and optimize the pyrolysis treatment for COPR by other organics.

Carbon dioxide capture using Sodium bicarbonate/Sodium carbonate supported on nanoporous Iron(III) oxide

NASA Astrophysics Data System (ADS)

Dutcher, Bryce

Strong evidence exists suggesting that anthropogenic emissions of CO 2, primarily from the combustion of fossil fuels, have been contributing to global climate change, including warming of the atmosphere and acidification of the oceans. These, in turn, lead to other effects such as melting of ice and snow cover, rising sea levels, severe weather patterns, and extinction of life forms. With these detrimental shifts in ecosystems already being observed, it becomes imperative to mitigate anthropogenic CO2. CO2 capture is typically a costly operation, usually due to the energy required for regeneration of the capture medium. Na2CO3 is one potential capture medium with the potential to decrease this energy requirement. Extensively researched as a potential sorbent for CO2, Na2CO3 is well known for its theoretically low energy requirement, due largely to its relatively low heat of reaction compared to other capture technologies. Its primary pitfalls, however, are its extremely low reaction rate during sorption and slow regeneration of Na2CO 3. Before Na2CO3 can be used as a CO2 sorbent, then, it is critical to increase its reaction rate. In order to do so, this project studied nanoporous FeOOH as a potential supporting material for Na2CO3. Because regeneration of the sorbent is the most energy-intensive step when using Na2CO3 for CO 2 sorption, this project focused on the decomposition of NaHCO 3, which is equivalent to CO2 desorption. Using BET, FTIR, XRD, XPS, SEM, TEM, magnetic susceptibility tests, and Mossbauer spectroscopy, we show FeOOH to be thermally stable both with and without the presence of NaHCO3 at temperatures necessary for sorption and regeneration, up to about 200°C. More significantly, we observe that FeOOH not only increases the surface area of NaHCO3, but also has a catalytic effect on the decomposition of NaHCO3, reducing activation energy from 80 kJ/mol to 44 kJ/mol. This reduction in activation energy leads to a significant increase in the reaction rate by a factor of nearly 50, which could translate into a substantial decrease in the cost of using Na2 CO3 for CO2 capture.

Solar Light Photocatalytic CO2 Reduction: General Considerations and Selected Bench-Mark Photocatalysts

PubMed Central

Neaţu, Ştefan; Maciá-Agulló, Juan Antonio; Garcia, Hermenegildo

2014-01-01

The reduction of carbon dioxide to useful chemicals has received a great deal of attention as an alternative to the depletion of fossil resources without altering the atmospheric CO2 balance. As the chemical reduction of CO2 is energetically uphill due to its remarkable thermodynamic stability, this process requires a significant transfer of energy. Achievements in the fields of photocatalysis during the last decade sparked increased interest in the possibility of using sunlight to reduce CO2. In this review we discuss some general features associated with the photocatalytic reduction of CO2 for the production of solar fuels, with considerations to be taken into account of the photocatalyst design, of the limitations arising from the lack of visible light response of titania, of the use of co-catalysts to overcome this shortcoming, together with several strategies that have been applied to enhance the photocatalytic efficiency of CO2 reduction. The aim is not to provide an exhaustive review of the area, but to present general aspects to be considered, and then to outline which are currently the most efficient photocatalytic systems. PMID:24670477

Solar light photocatalytic CO2 reduction: general considerations and selected bench-mark photocatalysts.

PubMed

Neațu, Stefan; Maciá-Agulló, Juan Antonio; Garcia, Hermenegildo

2014-03-25

The reduction of carbon dioxide to useful chemicals has received a great deal of attention as an alternative to the depletion of fossil resources without altering the atmospheric CO2 balance. As the chemical reduction of CO2 is energetically uphill due to its remarkable thermodynamic stability, this process requires a significant transfer of energy. Achievements in the fields of photocatalysis during the last decade sparked increased interest in the possibility of using sunlight to reduce CO2. In this review we discuss some general features associated with the photocatalytic reduction of CO2 for the production of solar fuels, with considerations to be taken into account of the photocatalyst design, of the limitations arising from the lack of visible light response of titania, of the use of co-catalysts to overcome this shortcoming, together with several strategies that have been applied to enhance the photocatalytic efficiency of CO2 reduction. The aim is not to provide an exhaustive review of the area, but to present general aspects to be considered, and then to outline which are currently the most efficient photocatalytic systems.

Electrochemical pretreatment of amino-carbon nanotubes on graphene support as a novel platform for bilirubin oxidase with improved bioelectrocatalytic activity towards oxygen reduction.

PubMed

Navaee, Aso; Salimi, Abdollah; Jafari, Fereydoon

2015-03-23

The electrochemical conditioning of amino-carbon nanotubes (CNTs) on a graphene support in an alkaline solution is used to produce -NHOH as hydrophilic functional groups for the efficient immobilization of bilirubin oxidase enzyme. The application of the immobilized enzyme for the direct electrocatalytic reduction of O2 is investigated. The onset potential of 0.81 V versus NHE and peak current density of 2.3 mA cm(-2) for rotating modified electrode at 1250 rpm, indicate improved biocatalytic activity of the proposed system for O2 reduction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygenates from Electrochemical Reduction of CO2.

PubMed

Feng, Guanghui; Chen, Wei; Wang, Baiyin; Song, Yanfang; Li, Guihua; Fang, Jianhui; Wei, Wei; Sun, Yuhan

2018-05-29

Electrochemical reduction of carbon dioxide (CO2) driven by renewable electricity to chemicals and fuels is considered as an ideal approach that can alleviate both carbon emission and energy tension stresses. High-value chemicals such as oxygenates can be effectively produced from CO2 electroreduction, which is highly attractive for the great promotion of the economy and applicability of CO2 utilization. This review focuses the recent advancements on the CO2 electrochemical reduction to formic acid, methanol, ethanol, acetic acid, and other oxygenates. The related principles, influence factors, and typical catalysts are summarized. On the basis of the aforementioned discussions, we present the future prospects for further development of CO2 electroreduction to oxygenates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Syngas Production from CO2 and H2 O in an Aqueous Photoelectrochemical Cell.

PubMed

Chu, Sheng; Fan, Shizhao; Wang, Yongjie; Rossouw, David; Wang, Yichen; Botton, Gianluigi A; Mi, Zetian

2016-11-07

Syngas, the mixture of CO and H 2 , is a key feedstock to produce methanol and liquid fuels in industry, yet limited success has been made to develop clean syngas production using renewable solar energy. We demonstrated that syngas with a benchmark turnover number of 1330 and a desirable CO/H 2 ratio of 1:2 could be attained from photoelectrochemical CO 2 and H 2 O reduction in an aqueous medium by exploiting the synergistic co-catalytic effect between Cu and ZnO. The CO/H 2 ratio in the syngas products was tuned in a large range between 2:1 and 1:4 with a total unity Faradaic efficiency. Moreover, a high Faradaic efficiency of 70 % for CO was acheived at underpotential of 180 mV, which is the lowest potential ever reported in an aqueous photoelectrochemical cell. It was found that the combination of Cu and ZnO offered complementary chemical properties that lead to special reaction channels not seen in Cu, or ZnO alone. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

CH4 production via CO2 reduction in a temperate bog - A source of (C-13)-depleted CH4

NASA Technical Reports Server (NTRS)

Lansdown, J. M.; Quay, P. D.; King, S. L.

1992-01-01

The paper reports measurements, taken over two annual cycles, of the flux and delta(C-13) of CH4 released from an acidic peat bog located in the foothills of the Cascade Range in Washington state, U.S. Measurements of the rate of aceticlastic methanogenesis and CO2 reduction in peat soil, using (C-14)-labeled acetate and sodium bicarbonate, show that acetate was not an important CH4 precursor and that CO2 reduction could account for all of the CH4 production. The in situ kinetic isotope effect for CO2 reduction, calculated using the delta-(C-13) of soil water CO2 and CH4 flux, was 0.932 +/- 0.007.

Ag, Co/graphene interactions and its effect on electrocatalytic oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Qaseem, Adnan; Chen, Fuyi; Wu, Xiaoqiang; Zhang, Nan; Xia, Zhenhai

2017-12-01

Silver nanoparticles supported on cobalt and nitrogen embedded reduced graphene oxide, Ag/Co-NGr, are synthesized by one-step hydrothermal route with remarkable catalytic activity for oxygen reduction reaction (ORR). As-synthesized electrocatalyst exhibits half-wave potential (0.82 V) comparable to commercial Pt/C (0.85 V), specific activity (0.45 mA cm-2) better than commercial Pt/C (0.35 mA cm-2) along with superior stability in alkaline environment (≈95% activity retention after 5000s compared to 80% for Pt/C). Moreover, Ag/Co-NGr is highly tolerant to methanol poisoning during ORR and delivers an excellent specific capacity of 789 mAh.g-1Zn with energy density of 947 Wh. kg-1 at a current density of 20 mA cm-2 in a Zn-air battery. For the first time, it is proven that particle size refinement and electronic perturbation of Ag nanoparticles take place due to metal-support interactions between Ag and Co/NGr. d-band center of Ag in Ag/Co-NGr upshifts toward the Fermi level with respect to the Ag/NGr as a result of charge transfer between Ag and Co/NGr. The superior catalytic activity and excellent stability of Ag/Co-NGr is attributed to the structural and electronic modification of Ag nanoparticles by Co and N elements on graphene.

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.

The Influence of Ozone Precursor Emissions from Four World Regions on Tropospheric Composition and Radiative Climate Forcing

NASA Technical Reports Server (NTRS)

Fry, Meridith; Naik, Vaishali; West, J. Jason; Schwarzkopf, M. Daniel; Fiore, Arlene M.; Collins, William J.; Dentener, Frank J.; Shindell, Drew T.; Atherton, Cyndi; Bergmann, Daniel;

Noncovalent immobilization of electrocatalysts on carbon electrodes for fuel production.

PubMed

Blakemore, James D; Gupta, Ayush; Warren, Jeffrey J; Brunschwig, Bruce S; Gray, Harry B

2013-12-11

We show that molecular catalysts for fuel-forming reactions can be immobilized on graphitic carbon electrode surfaces via noncovalent interactions. A pyrene-appended bipyridine ligand (P) serves as the linker between each complex and the surface. Immobilization of a rhodium proton-reduction catalyst, [Cp*Rh(P)Cl]Cl (1), and a rhenium CO2-reduction catalyst, Re(P)(CO)3Cl (2), afford electrocatalytically active assemblies. X-ray photoelectron spectroscopy and electrochemistry confirm catalyst immobilization. Reduction of 1 in the presence of p-toluenesulfonic acid results in catalytic H2 production, while reduction of 2 in the presence of CO2 results in catalytic CO production.

Novel MOF-Derived Co@N-C Bifunctional Catalysts for Highly Efficient Zn-Air Batteries and Water Splitting.

PubMed

Zhang, Mingdao; Dai, Quanbin; Zheng, Hegen; Chen, Mindong; Dai, Liming

2018-03-01

Metal-organic frameworks (MOFs) and MOF-derived materials have recently attracted considerable interest as alternatives to noble-metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N-C materials (C-MOF-C2-T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C-MOF-C2-900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N-doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO 2 , respectively. Primary Zn-air batteries based on C-MOF-900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g Zn -1 under 10 mA cm -2 . Rechargeable Zn-air batteries based on C-MOF-C2-900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm -2 ), along with an excellent cycling stability with no increase in polarization even after 120 h - outperform their counterparts based on noble-metal-based air electrodes. The resultant rechargeable Zn-air batteries are used to efficiently power electrochemical water-splitting systems, demonstrating promising potential as integrated green energy systems for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formate production through biocatalysis

PubMed Central

Alissandratos, Apostolos; Kim, Hye-Kyung; Easton, Christopher J

2013-01-01

The generation of formate from CO2 provides a method for sequestration of this greenhouse gas as well as the production of a valuable commodity chemical and stabilized form of hydrogen fuel. Formate dehydrogenases are enzymes with the potential to catalyze this reaction; however they generally favor the reverse process, i.e., formate oxidation. By contrast, the formate dehydrogenase of the acetogen Clostridium carboxidivorans has been found to preferentially catalyze the reduction of CO2. This is in accord with its natural role to introduce CO2 as a carbon source in the Wood-Ljungdahl pathway. The direction of catalysis derives from the enzyme’s low affinity for formate. This enzyme is therefore an excellent candidate for biotechnological applications aimed at producing formic acid and derivative chemicals from CO2. PMID:23841981

Development of air conditioning technologies to reduce CO2 emissions in the commercial sector

PubMed Central

Yoshida, Yukiko

2006-01-01

Background Architectural methods that take into account global environmental conservation generally concentrate on mitigating the heat load of buildings. Here, we evaluate the reduction of carbon dioxide (CO2) emissions that can be achieved by improving heating, ventilating, and air conditioning (HVAC) technologies. Results The Climate Change Research Hall (CCRH) of the National Institute for Environmental Studies (NIES) is used as a case study. CCRH was built in line with the "Green Government Buildings" program of the Government Buildings Department at the Ministry of Land, Infrastructure and Transport in Japan. We have assessed the technology used in this building, and found that there is a possibility to reduce energy consumption in the HVAC system by 30%. Conclusion Saving energy reduces CO2 emissions in the commercial sector, although emission factors depend on the country or region. Consequently, energy savings potential may serve as a criterion in selecting HVAC technologies with respect to emission reduction targets. PMID:17062161

A Probabilistic System Analysis of Intelligent Propulsion System Technologies

NASA Technical Reports Server (NTRS)

Tong, Michael T.

2007-01-01

NASA s Intelligent Propulsion System Technology (Propulsion 21) project focuses on developing adaptive technologies that will enable commercial gas turbine engines to produce fewer emissions and less noise while increasing reliability. It features adaptive technologies that have included active tip-clearance control for turbine and compressor, active combustion control, turbine aero-thermal and flow control, and enabling technologies such as sensors which are reliable at high operating temperatures and are minimally intrusive. A probabilistic system analysis is performed to evaluate the impact of these technologies on aircraft CO2 (directly proportional to fuel burn) and LTO (landing and takeoff) NO(x) reductions. A 300-passenger aircraft, with two 396-kN thrust (85,000-pound) engines is chosen for the study. The results show that NASA s Intelligent Propulsion System technologies have the potential to significantly reduce the CO2 and NO(x) emissions. The results are used to support informed decisionmaking on the development of the intelligent propulsion system technology portfolio for CO2 and NO(x) reductions.

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.

Compact, Lightweight Adsorber and Sabatier Reactor for CO2 Capture and Reduction for Consumable and Propellant Production

NASA Technical Reports Server (NTRS)

Junaedi, Christian; Hawley, Kyle; Walsh, Dennis; Roychoudhury, Subir; Busby, Stacy A.; Abney, Morgan B.; Perry, Jay L.; Knox, James C.

2012-01-01

The utilization of CO2 to produce (or recycle) life support consumables, such as O2 and H2O, and to generate propellant fuels is an important aspect of NASA's concept for future, long duration planetary exploration. One potential approach is to capture and use CO2 from the Martian atmosphere to generate the consumables and propellant fuels. Precision Combustion, Inc. (PCI), with support from NASA, continues to develop its regenerable adsorber technology for capturing CO2 from gaseous atmospheres (for cabin atmosphere revitalization and in-situ resource utilization applications) and its Sabatier reactor for converting CO2 to methane and water. Both technologies are based on PCI's Microlith(R) substrates and have been demonstrated to reduce size, weight, and power consumption during CO2 capture and methanation process. For adsorber applications, the Microlith substrates offer a unique resistive heating capability that shows potential for short regeneration time and reduced power requirements compared to conventional systems. For the Sabatier applications, the combination of the Microlith substrates and durable catalyst coating permits efficient CO2 methanation that favors high reactant conversion, high selectivity, and durability. Results from performance testing at various operating conditions will be presented. An effort to optimize the Sabatier reactor and to develop a bench-top Sabatier Development Unit (SDU) will be discussed.

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

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Superexchange Effects on Oxygen Reduction Activity of Edge-Sharing [Cox Mn1-x O6 ] Octahedra in Spinel Oxide.

PubMed

Zhou, Ye; Sun, Shengnan; Xi, Shibo; Duan, Yan; Sritharan, Thirumany; Du, Yonghua; Xu, Zhichuan J

2018-03-01

Mn-Co containing spinel oxides are promising, low-cost electrocatalysts for the oxygen reduction reaction (ORR). Most studies are devoted to the design of porous Mn-Co spinels or to strongly coupled hybrids (e.g., MnCo 2 O 4 /N-doped-rmGO) to maximize the mass efficiency. The lack of analyses by metal oxide intrinsic activity (activity normalized to catalysts' surface area) hinders the development of fundamental understanding of the physicochemical principles behind the catalytic activities. A systematic study on the composition dependence of ORR in ZnCo x Mn 2- x O 4 (x = 0.0-2.0) spinel is presented here with special attention to the role of edge sharing [Co x Mn 1- x O 6 ] octahedra in the spinel structure. The ORR specific activity of ZnCo x Mn 2- x O 4 spans across a potential window of 200 mV, indicating an activity difference of ≈3 orders of magnitude. The curve of composition-dependent ORR specific activity as a function of Co substitution exhibits a volcano shape with an optimum Mn/Co ratio of 0.43. It is revealed that the modulated e g occupancy of active Mn cations (0.3-0.9), as a consequence of the superexchange effect between edge sharing [CoO 6 ] and [MnO 6 ], reflects the ORR activity of edge sharing [Co x Mn 1- x O 6 ] octahedra in the ZnCo x Mn 2- x O 4 spinel oxide. These findings offer crucial insights in designing spinel oxide catalysts with fine-tuned e g occupancy for efficient catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical absorption and CO2 biofixation via the cultivation of Spirulina in semicontinuous mode with nutrient recycle.

PubMed

da Rosa, Gabriel Martins; Moraes, Luiza; Cardias, Bruna Barcelos; de Souza, Michele da Rosa Andrade Zimmermann; Costa, Jorge Alberto Vieira

2015-09-01

The chemical absorption of carbon dioxide (CO2) is a technique used for the mitigation of the greenhouse effect. However, this process consumes high amounts of energy to regenerate the absorbent and to separate the CO2. CO2 removal by microalgae can be obtained via the photosynthesis process. The objective of this study was to investigate the cultivation and the macromolecules production by Spirulina sp. LEB 18 with the addition of monoethanolamine (MEA) and CO2. In the cultivation with MEA, were obtained higher results of specific growth rate, biomass productivity, CO2 biofixation, CO2 use efficiency, and lower generation time. Besides this, the carbohydrate concentration obtained at the end of this assay was approximately 96.0% higher than the control assay. Therefore, Spirulina can be produced using medium recycle and the addition of MEA, thereby promoting the reduction of CO2 emissions and showing potential for areas that require higher concentrations of carbohydrates, such as in bioethanol production. Copyright © 2015 Elsevier Ltd. All rights reserved.

No catalyst addition and highly efficient dissociation of H2O for the reduction of CO2 to formic acid with Mn.

PubMed

Lyu, Lingyun; Zeng, Xu; Yun, Jun; Wei, Feng; Jin, Fangming

2014-05-20

The "greenhouse effect" caused by the increasing atmospheric CO2 level is becoming extremely serious, and thus, the reduction of CO2 emissions has become an extensive, urgent, and long-term task. The dissociation of water for CO2 reduction with solar energy is regarded as one of the most promising methods for the sustainable development of the environment and energy. However, a high solar-to-fuel efficiency keeps a great challenge. In this work, the first observation of a highly effective, highly selective, and robust system of dissociating water for the reduction of carbon dioxide (CO2) into formic acid with metallic manganese (Mn) is reported. A considerably high formic acid yield of more than 75% on a carbon basis from NaHCO3 was achieved with 98% selectivity in the presence of simple commercially available Mn powder without the addition of any catalyst, and the proposed process is exothermic. Thus, this study may provide a promising method for the highly efficient dissociation of water for CO2 reduction by combining solar-driven thermochemistry with the reduction of MnO into Mn.

CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane.

PubMed

Khadka, Nimesh; Dean, Dennis R; Smith, Dayle; Hoffman, Brian M; Raugei, Simone; Seefeldt, Lance C

2016-09-06

The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO(-)) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ("direct hydride transfer" reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ("associative" reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70(Val→Ala), α-195(His→Gln)) are found to significantly alter the distribution of products between formate and CO/CH4.

Iron: A Biogeochemical Engine That Drives Carbon, Nitrogen, and Phosphorus Cycling in Humid Tropical Forest Soils

NASA Astrophysics Data System (ADS)

Silver, W. L.; Hall, S. J.; Thompson, A.; Yang, W. H.

2014-12-01

The abundance of redox active Fe minerals has the potential to alter the storage and loss of C, contribute to gaseous N emissions, and control P retention in upland tropical forest soils. High concentrations of short-range order Fe minerals led to Fe(II) production rates of 26-206 μg g d-1 under short-term low redox conditions (Chacón et al. 2006, Liptzin and Silver 2009, Dubinsky et al. 2010). Potential C mineralization from Fe(II) reduction was 34-263 g CO2-C m-2 y-1, C losses equivalent to approximately 10-60 % of annual litterfall production in this forest. Decreased acidity during Fe reduction can destabilize soil aggregates and lead to C losses. Iron is rapidly reoxidized during aerobic periods, which can subsequently lead to C stabilization via complexation reactions. Fe oxidation can also stimulate C losses via pH-driven dissolved organic C production and directly via Fenton reactions. In laboratory experiments, rates of CO2 production were strongly linearly correlated with Fe(II) loss under aerobic conditions, increasing by 0.51 ± 0.02 µg CO2-C g soil h-1 respired for each mg of Fe(II) g-1 soil oxidized or sorbed (Hall and Silver 2013). Iron oxidation has also been linked to dissimilatory NO3- reduction to NH4+ leading to N retention in ecosystems. Fe(III) reduction coupled with NH4+ oxidation (Feammox) can lead to N losses as dinitrogen gas (N2) or nitrous oxide (N2O), a potent greenhouse gas. Estimates suggest that Feammox resulted in gaseous N losses of 1-4 kg N ha-1 y-1 (Yang et al. 2012), rates equivalent to total denitrification in this forest. Oxidized Fe can strongly bind P decreasing it's availability to plant roots. While this is commonly cited as a potential limitation to net primary production in tropical forests, it also helps to retain P in ecosystems with high rainfall and potential leaching losses. Microbial biomass P availability increased significantly with Fe(II) production, suggesting the P mobilized during Fe(II) reduction was rapidly immobilized into biological pools (Liptzin and Silver 2009). Data suggest that Fe-redox cycling may decrease P limitation to NPP, and help maintain forest nutrient stocks. In summary, our results highlight the biogeochemical significance of Fe cycling in upland soils environments and its important role in the dynamics of humid tropical forests.

Platinized tin oxide catalysts for CO2 lasers: Effects of pretreatment

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Upchurch, Billy T.

1990-01-01

Platinized tin oxide surfaces used for low-temperature CO oxidation in CO2 lasers have been characterized before and after reduction in CO at 125 and 250 C using ion scattering spectroscopy (ISS) and X ray photoelectron spectroscopy (XPS). XPS indicates that the Pt is present initially as PtO2. Reduction at 125 C converts the PtO2 to Pt(OH)2 while reduction at 250 C converts the PtO2 to metallic Pt. ISS shows that the Pt in the outermost atomic layer of the catalyst is mostly covered by substrate species during the 250 C reduction. Both the ISS and XPS results are consistent with Pt/Sn alloy formation. The surface dehydration and migration of substrate species over surface Pt and Sn appear to explain why a CO pretreatment at 250 C produces inferior CO oxidation activities compared to a 125 C pretreatment.

Platinized tin oxide catalysts for CO2 lasers - Effects of pretreatment

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Upchurch, Billy T.

1989-01-01

Platinized tin oxide surfaces used for low-temperature CO oxidation in CO2 lasers have been characterized before and after reduction in CO at 125 and 250 C using ion scattering spectroscopy (ISS) and X-ray photoelectron spectroscopy (XPS). XPS indicates that the Pt is present initially as Pto2. Reduction at 125 C converts the PtO2 to Pt(OH)2 while reduction at 250 C converts the PtO2 to metallic Pt. ISS shows that the Pt in the outermost atomic layer of the catalyst is mostly covered by substrate species during the 250 C reduction. Both the ISS and XPS results are consistent with Pt/Sn alloy formation. The surface dehydration and migration of substrate species over surface Pt and Sn appear to explain why a CO pretreatment at 250 C produces inferior CO oxidation activities compared to a 125 C pretreatment.

Activities of Combined TiO2 Semiconductor Nanocatalysts Under Solar Light on the Reduction of CO2.

PubMed

Liu, Hongfang; Dao, Anh Quang; Fu, Chaoyang

2016-04-01

The materials based on TiO2 semiconductors are a promising option for electro-photocatalytic systems working as solar energy low-carbon fuels exchanger. These materials' structures are modified by doping metals and metal oxides, by metal sulfides sensitization, or by graphene supported membrane, enhancing their catalytic activity. The basic phenomenon of CO2 reduction to CH4 on Pd modified TiO2 under UV irradiation could be enhanced by Pd, or RuO2 co-doped TiO2. Sensitization with metal sulfide QDs is effective by moving of photo-excited electron from QDs to TiO2 particles. Based on characteristics of the catalysts various combinations of catalysts are proposed in order to creat catalyst systems with good CO2 reduction efficiency. From this critical review of the CO2 reduction to organic compounds by converting solar light and CO2 to storable fuels it is clear that more studies are still attractive and needed.

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

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

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

DOE PAGES

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.; ...

2017-07-03

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Hydrogenation of organic matter as a terminal electron sink sustains high CO 2 :CH 4 production ratios during anaerobic decomposition

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

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO2 and CH4 for each molecule of organic matter degraded. However, CO2:CH4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO2 has an oxidation state of +4, if CH4more » (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO2:CH4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. This mechanism for CO2 generation without concomitant CH4 production has the potential to regulate the global warming potential of peatlands by elevating CO2:CH4 production ratios.« 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

Roles of the Lewis acid and base in the chemical reduction of CO2 catalyzed by frustrated Lewis pairs.

PubMed

Lim, Chern-Hooi; Holder, Aaron M; Hynes, James T; Musgrave, Charles B

2013-09-03

We employ quantum chemical calculations to discover how frustrated Lewis pairs (FLP) catalyze the reduction of CO2 by ammonia borane (AB); specifically, we examine how the Lewis acid (LA) and Lewis base (LB) of an FLP activate CO2 for reduction. We find that the LA (trichloroaluminum, AlCl3) alone catalyzes hydride transfer (HT) to CO2 while the LB (trimesitylenephosphine, PMes3) actually hinders HT; inclusion of the LB increases the HT barrier by ∼8 kcal/mol relative to the reaction catalyzed by LAs only. The LB hinders HT by donating its lone pair to the LUMO of CO2, increasing the electron density on the C atom and thus lowering its hydride affinity. Although the LB hinders HT, it nonetheless plays a crucial role by stabilizing the active FLP·CO2 complex relative to the LA dimer, free CO2, and free LB. This greatly increases the concentration of the reactive complex in the form FLP·CO2 and thus increases the rate of reaction. We expect that the principles we describe will aid in understanding other catalytic CO2 reductions.

Untangling the confusion around land carbon science and climate change mitigation policy

NASA Astrophysics Data System (ADS)

Mackey, Brendan; Prentice, I. Colin; Steffen, Will; House, Joanna I.; Lindenmayer, David; Keith, Heather; Berry, Sandra

2013-06-01

Depletion of ecosystem carbon stocks is a significant source of atmospheric CO2 and reducing land-based emissions and maintaining land carbon stocks contributes to climate change mitigation. We summarize current understanding about human perturbation of the global carbon cycle, examine three scientific issues and consider implications for the interpretation of international climate change policy decisions, concluding that considering carbon storage on land as a means to 'offset' CO2 emissions from burning fossil fuels (an idea with wide currency) is scientifically flawed. The capacity of terrestrial ecosystems to store carbon is finite and the current sequestration potential primarily reflects depletion due to past land use. Avoiding emissions from land carbon stocks and refilling depleted stocks reduces atmospheric CO2 concentration, but the maximum amount of this reduction is equivalent to only a small fraction of potential fossil fuel emissions.

Subtask 1.22 - Microbial Cycling of CH4, CO2, and N2O in a Wetlands Environment

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

Dingyi Ye; Bethany Kurz; Marc Kurz

Soil microbial metabolic activities play an important role in determining CO{sub 2}, CH{sub 4}, and N{sub 2}O fluxes from terrestrial ecosystems. To verify and evaluate CO{sub 2} sequestration potential by wetland restoration in the Prairie Pothole Region (PPR), as well as to address concern over restoration effects on CH{sub 4} and N{sub 2}O emissions, laboratory and in situ microcosm studies on microbial cycling of CO{sub 2}, CH{sub 4}, and N{sub 2}O were initiated. In addition, to evaluate the feasibility of the use of remote sensing to detect soil gas flux from wetlands, a remote-sensing investigation was also conducted. Results ofmore » the laboratory microcosm study unequivocally proved that restoration of PPR wetlands does sequester atmospheric CO{sub 2}. Under the experimental conditions, the simulated restored wetlands did not promote neither N{sub 2}O nor CH{sub 4} fluxes. Application of ammonia enhanced both N{sub 2}O and CH{sub 4} emission, indicating that restoration of PPR wetlands may reduce both N{sub 2}O and CH{sub 4} emission by cutting N-fertilizer input. Enhancement of CO{sub 2} emission by the N-fertilizer was observed, and this observation revealed an overlooked fact that application of N-fertilizer may potentially increase CO{sub 2} emission. In addition, the CO{sub 2} results also demonstrate that wetland restoration sequesters atmospheric carbon not only by turning soil conditions from aerobic to anoxic, but also by cutting N-fertilizer input that may enhance CO{sub 2} flux. The investigation on microbial community structure and population dynamics showed that under the experimental conditions restoration of the PPR wetlands would not dramatically increase population sizes of those microorganisms that produce N{sub 2}O and CH{sub 4}. Results of the in situ study proved that restoration of the PPR wetland significantly reduced CO{sub 2} flux. Ammonia enhanced the greenhouse gas emission and linearly correlated to the CO{sub 2} flux within the experimental rate range (46-200 kg N ha{sup -1}). The results also clarified that the overall reduction in global warming potential (GWP) by the PPR wetland restoration was mainly contributed from reduction in CO{sub 2} flux. These results demonstrate that restoration of currently farmed PPR wetlands will significantly reduce the overall GWP budget. Remote sensing investigations indicate that while the 15-meter resolution of the imagery was sufficient to delineate multiple zones in larger wetlands, it was not sufficient for correlation with the ground-based gas flux measurement data, which were collected primarily for smaller wetland sites (<250 meters) in the areas evaluated by this task. To better evaluate the feasibility of using satellite imagery to quantify wetland gas flux, either higher-resolution satellite imagery or gas flux data from larger wetland sites is needed.« less

Potential of wind power projects under the Clean Development Mechanism in India

PubMed Central

Purohit, Pallav; Michaelowa, Axel

2007-01-01

Background So far, the cumulative installed capacity of wind power projects in India is far below their gross potential (≤ 15%) despite very high level of policy support, tax benefits, long term financing schemes etc., for more than 10 years etc. One of the major barriers is the high costs of investments in these systems. The Clean Development Mechanism (CDM) of the Kyoto Protocol provides industrialized countries with an incentive to invest in emission reduction projects in developing countries to achieve a reduction in CO2 emissions at lowest cost that also promotes sustainable development in the host country. Wind power projects could be of interest under the CDM because they directly displace greenhouse gas emissions while contributing to sustainable rural development, if developed correctly. Results Our estimates indicate that there is a vast theoretical potential of CO2 mitigation by the use of wind energy in India. The annual potential Certified Emissions Reductions (CERs) of wind power projects in India could theoretically reach 86 million. Under more realistic assumptions about diffusion of wind power projects based on past experiences with the government-run programmes, annual CER volumes by 2012 could reach 41 to 67 million and 78 to 83 million by 2020. Conclusion The projections based on the past diffusion trend indicate that in India, even with highly favorable assumptions, the dissemination of wind power projects is not likely to reach its maximum estimated potential in another 15 years. CDM could help to achieve the maximum utilization potential more rapidly as compared to the current diffusion trend if supportive policies are introduced. PMID:17663772

Protective effects of kolaviron and gallic acid against cobalt-chloride-induced cardiorenal dysfunction via suppression of oxidative stress and activation of the ERK signaling pathway.

PubMed

Akinrinde, Akinleye Stephen; Omobowale, Olutayo; Oyagbemi, Ademola; Asenuga, Ebunoluwa; Ajibade, Temitayo

2016-12-01

Cobalt (Co) toxicity is a potential public health problem due to recent renewed use of Co in orthopedic implants, dietary supplements, and blood doping in athletes and horses. We investigated the protective roles of kolaviron (KV), a bi-flavonoid of Garcinia kola, and gallic acid (GA) on cobalt chloride (CoCl 2 )-induced cardiorenal damage in rats. CoCl 2 caused significant increases (p < 0.05) in serum creatine kinase-myocardial band (CK-MB), lactate dehydrogenase (LDH), aspartate transaminase (AST), xanthine oxidase (XO), urea, creatinine, malondialdehyde, H 2 O 2 , nitric oxide, as well as C-reactive protein expression, along with significant (p < 0.05) reduction in cardiac and renal expression of extracellular signal regulated kinase (ERK) and the activities of superoxide dismutase, catalase, and glutathione S-transferase. KV and GA prevented the toxic effects of CoCl 2 by stimulating ERK expression and reversing Co-induced biochemical changes. Administration of CoCl 2 alone did not significantly alter ECG patterns in the rats, although co-treatment with KV (200 mg/kg) produced QT-segment prolongation and also appeared to potentiate Co hypotension. Histopathology of the heart and kidneys of rats treated with KV and GA confirmed the biochemical data. KV and GA thus protected against cardiac and renal damage in Co intoxication via antioxidant and (or) cell survival mechanisms, possibly involving ERK activation.

Projected pH reductions by 2100 might put deep North Atlantic biodiversity at risk

NASA Astrophysics Data System (ADS)

Gehlen, M.; Séférian, R.; Jones, D. O. B.; Roy, T.; Roth, R.; Barry, J.; Bopp, L.; Doney, S. C.; Dunne, J. P.; Heinze, C.; Joos, F.; Orr, J. C.; Resplandy, L.; Segschneider, J.; Tjiputra, J.

2014-06-01

This study aims at evaluating the potential for impacts of ocean acidification on North Atlantic deep-sea ecosystems in response to IPCC AR5 Representative Concentration Pathways (RCP). Deep-sea biota is likely highly vulnerable to changes in seawater chemistry and sensitive to moderate excursions in pH. Here we show, from seven fully-coupled Earth system models, that for three out of four RCPs over 17% of the seafloor area below 500 m depth in the North Atlantic sector will experience pH reductions exceeding -0.2 units by 2100. Increased stratification in response to climate change partially alleviates the impact of ocean acidification on deep benthic environment. We report major potential consequences of pH reductions for deep-sea biodiversity hotspots, such as seamounts and canyons. By 2100 and under the high CO2 scenario RCP8.5 pH reductions exceeding -0.2, (respectively -0.3) units are projected in close to 23% (~ 15%) of North Atlantic deep-sea canyons and ~ 8% (3%) of seamounts - including seamounts proposed as sites of marine protected areas. The spatial pattern of impacts reflects the depth of the pH perturbation and does not scale linearly with atmospheric CO2 concentration. Impacts may cause negative changes of the same magnitude or exceeding the current target of 10% of preservation of marine biomes set by the convention on biological diversity implying that ocean acidification may offset benefits from conservation/management strategies relying on the regulation of resource exploitation.

Promoting Ethylene Selectivity from CO2 Electroreduction on CuO Supported onto CO2 Capture Materials.

PubMed

Yang, Hui-Juan; Yang, Hong; Hong, Yu-Hao; Zhang, Peng-Yang; Wang, Tao; Chen, Li-Na; Zhang, Feng-Yang; Wu, Qi-Hui; Tian, Na; Zhou, Zhi-You; Sun, Shi-Gang

2018-03-09

Cu is a unique catalyst for CO 2 electroreduction, since it can catalyze CO 2 reduction to a series of hydrocarbons, alcohols, and carboxylic acids. Nevertheless, such Cu catalysts suffer from poor selectivity. High pressure of CO 2 is considered to facilitate the activity and selectivity of CO 2 reduction. Herein, a new strategy is presented for CO 2 reduction with improved C 2 H 4 selectivity on a Cu catalyst by using CO 2 capture materials as the support at ambient pressure. N-doped carbon (N x C) was synthesized through high-temperature carbonization of melamine and l-lysine. We observed that the CO 2 uptake capacity of N x C depends on both the microporous area and the content of pyridinic N species, which can be controlled by the carbonization temperature (600-800 °C). The as-prepared CuO/N x C catalysts exhibit a considerably higher C 2 H 4 faradaic efficiency (36 %) than CuO supported on XC-72 carbon black (19 %), or unsupported CuO (20 %). Moreover, there is a good linear relationship between the C 2 H 4 faradaic efficiency and CO 2 uptake capacity of the supports for CuO. The local high CO 2 concentration near Cu catalysts, created by CO 2 capture materials, was proposed to increase the coverage of CO intermediate, which is favorable for the coupling of two CO units in the formation of C 2 H 4 . This study demonstrates that pairing Cu catalysts with CO 2 capture supports is a promising approach for designing highly effective CO 2 reduction electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene-Immobilized fac-Re(bipy)(CO)3Cl for Syngas Generation from Carbon Dioxide.

PubMed

Zhou, Xin; Micheroni, Daniel; Lin, Zekai; Poon, Christopher; Li, Zhong; Lin, Wenbin

2016-02-17

We report the synthesis of fac-M(4-amino-bipy)(CO)3X (M = Mn and X = Br or M = Re and X = Cl, with bipy = 2,2'-bipyridine), their immobilization on graphene oxide (GrO) via diazonium grafting, and the use of Re-functionalized GrO for electrocatalytic syngas production. Infrared (IR) spectroscopy, X-ray absorption fine structure (XAFS) spectroscopy, and electrocatalysis indicated successful grafting of the Re catalyst onto GrO. Re-functionalized GrO was then deposited onto a glassy carbon electrode (GCE) for CO2 reduction. Investigation of the Re-functionalized GCE for syngas production was performed in a CO2-saturated acetonitrile solution with 3.1 M H2O as the proton source and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte. Cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatography (GC) were employed to determine its CO2-to-CO conversion performance. The Re catalyst shows a turnover frequency (TOF) for generating CO up to 4.44 s(-1) with a CO/H2 ratio of 7:5.

Increases in desert shrub productivity under elevated carbon dioxide vary with water availability

USGS Publications Warehouse

Housman, D.C.; Naumburg, E.; Huxman, T. E.; Charlet, T.N.; Nowak, R.S.; Smith, S.D.

2006-01-01

Productivity of aridland plants is predicted to increase substantially with rising atmospheric carbon dioxide (CO2) concentrations due to enhancement in plant water-use efficiency (WUE). However, to date, there are few detailed analyses of how intact desert vegetation responds to elevated CO2. From 1998 to 2001, we examined aboveground production, photosynthesis, and water relations within three species exposed to ambient (around 38 Pa) or elevated (55 Pa) CO2 concentrations at the Nevada Desert Free-Air CO2 Enrichment (FACE) Facility in southern Nevada, USA. The functional types sampled - evergreen (Larrea tridentata), drought-deciduous (Ambrosia dumosa), and winter-deciduous shrubs (Krameria erecta) - represent potentially different responses to elevated CO2 in this ecosystem. We found elevated CO2 significantly increased aboveground production in all three species during an anomalously wet year (1998), with relative production ratios (elevated:ambient CO2) ranging from 1.59 (Krameria) to 2.31 (Larrea). In three below-average rainfall years (1999-2001), growth was much reduced in all species, with only Ambrosia in 2001 having significantly higher production under elevated CO2. Integrated photosynthesis (mol CO2 m-2 y-1) in the three species was 1.26-2.03-fold higher under elevated CO2 in the wet year (1998) and 1.32-1.43-fold higher after the third year of reduced rainfall (2001). Instantaneous WUE was also higher in shrubs grown under elevated CO2. The timing of peak canopy development did not change under elevated CO2; for example, there was no observed extension of leaf longevity into the dry season in the deciduous species. Similarly, seasonal patterns in CO2 assimilation did not change, except for Larrea. Therefore, phenological and physiological patterns that characterize Mojave Desert perennials - early-season lags in canopy development behind peak photosynthetic capacity, coupled with reductions in late-season photosynthetic capacity prior to reductions in leaf area - were not significantly affected by elevated CO2. Together, these findings suggest that elevated CO2 can enhance the productivity of Mojave Desert shrubs, but this effect is most pronounced during years with abundant rainfall when soil resources are most available. ?? 2006 Springer Science+Business Media, Inc.

Toward Quantitatively Accurate Calculation of the Redox-Associated Acid–Base and Ligand Binding Equilibria of Aquacobalamin

DOE PAGES

Johnston, Ryne C.; Zhou, Jing; Smith, Jeremy C.; ...

2016-07-08

In redox processes in complex transition metal-containing species are often intimately associated with changes in ligand protonation states and metal coordination number. Moreover, a major challenge is therefore to develop consistent computational approaches for computing pH-dependent redox and ligand dissociation properties of organometallic species. Reduction of the Co center in the vitamin B12 derivative aquacobalamin can be accompanied by ligand dissociation, protonation, or both, making these properties difficult to compute accurately. We examine this challenge here by using density functional theory and continuum solvation to compute Co ligand binding equilibrium constants (Kon/off), pKas and reduction potentials for models of aquacobalaminmore » in aqueous solution. We consider two models for cobalamin ligand coordination: the first follows the hexa, penta, tetra coordination scheme for Co III, Co II, and Co I species, respectively, and the second model features saturation of each vacant axial coordination site on Co II and Co I species with a single, explicit water molecule to maintain six directly interacting ligands or water molecules in each oxidation state. Comparing these two coordination schemes in combination with five dispersion-corrected density functionals, we find that the accuracy of the computed properties is largely independent of the scheme used, but including only a continuum representation of the solvent yields marginally better results than saturating the first solvation shell around Co throughout. PBE performs best, displaying balanced accuracy and superior performance overall, with RMS errors of 80 mV for seven reduction potentials, 2.0 log units for five pK as and 2.3 log units for two log K on/off values for the aquacobalamin system. Furthermore, we find that the BP86 functional commonly used in corrinoid studies suffers from erratic behavior and inaccurate descriptions of Co axial ligand binding, leading to substantial errors in predicted pK as and K on/off values. Finally, these findings demonstrate the effectiveness of the present approach for computing electrochemical and thermodynamic properties of a complex transition metal-containing cofactor.« less

Simulated effect of calcification feedback on atmospheric CO2 and ocean acidification

PubMed Central

Zhang, Han; Cao, Long

2016-01-01

Ocean uptake of anthropogenic CO2 reduces pH and saturation state of calcium carbonate materials of seawater, which could reduce the calcification rate of some marine organisms, triggering a negative feedback on the growth of atmospheric CO2. We quantify the effect of this CO2-calcification feedback by conducting a series of Earth system model simulations that incorporate different parameterization schemes describing the dependence of calcification rate on saturation state of CaCO3. In a scenario with SRES A2 CO2 emission until 2100 and zero emission afterwards, by year 3500, in the simulation without CO2-calcification feedback, model projects an accumulated ocean CO2 uptake of 1462 PgC, atmospheric CO2 of 612 ppm, and surface pH of 7.9. Inclusion of CO2-calcification feedback increases ocean CO2 uptake by 9 to 285 PgC, reduces atmospheric CO2 by 4 to 70 ppm, and mitigates the reduction in surface pH by 0.003 to 0.06, depending on the form of parameterization scheme used. It is also found that the effect of CO2-calcification feedback on ocean carbon uptake is comparable and could be much larger than the effect from CO2-induced warming. Our results highlight the potentially important role CO2-calcification feedback plays in ocean carbon cycle and projections of future atmospheric CO2 concentrations. PMID:26838480

Metal/Carbon Hybrid Nanostructures Produced from Plasma-Enhanced Chemical Vapor Deposition over Nafion-Supported Electrochemically Deposited Cobalt Nanoparticles

PubMed Central

Achour, Amine; Saeed, Khalid; Djouadi, Mohamed Abdou

2018-01-01

In this work, we report development of hybrid nanostructures of metal nanoparticles (NP) and carbon nanostructures with strong potential for catalysis, sensing, and energy applications. First, the etched silicon wafer substrates were passivated for subsequent electrochemical (EC) processing through grafting of nitro phenyl groups using para-nitrobenzene diazonium (PNBT). The X-ray photoelectron spectroscope (XPS) and atomic force microscope (AFM) studies confirmed presence of few layers. Cobalt-based nanoparticles were produced over dip or spin coated Nafion films under different EC reduction conditions, namely CoSO4 salt concentration (0.1 M, 1 mM), reduction time (5, 20 s), and indirect or direct EC reduction route. Extensive AFM examination revealed NP formation with different attributes (size, distribution) depending on electrochemistry conditions. While relatively large NP with >100 nm size and bimodal distribution were obtained after 20 s EC reduction in H3BO3 following Co2+ ion uptake, ultrafine NP (<10 nm) could be produced from EC reduction in CoSO4 and H3BO3 mixed solution with some tendency to form oxides. Different carbon nanostructures including few-walled or multiwalled carbon nanotubes (CNT) and carbon nanosheets were grown in a C2H2/NH3 plasma using the plasma-enhanced chemical vapor deposition technique. The devised processing routes enable size controlled synthesis of cobalt nanoparticles and metal/carbon hybrid nanostructures with unique microstructural features. PMID:29702583

Ratcheting ambition to limit warming to 1.5 °C–trade-offs between emission reductions and carbon dioxide removal

NASA Astrophysics Data System (ADS)

Holz, Christian; Siegel, Lori S.; Johnston, Eleanor; Jones, Andrew P.; Sterman, John

2018-06-01

Mitigation scenarios to limit global warming to 1.5 °C or less in 2100 often rely on large amounts of carbon dioxide removal (CDR), which carry significant potential social, environmental, political and economic risks. A precautionary approach to scenario creation is therefore indicated. This letter presents the results of such a precautionary modelling exercise in which the models C-ROADS and En-ROADS were used to generate a series of 1.5 °C mitigation scenarios that apply increasingly stringent constraints on the scale and type of CDR available. This allows us to explore the trade-offs between near-term stringency of emission reductions and assumptions about future availability of CDR. In particular, we find that regardless of CDR assumptions, near-term ambition increase (‘ratcheting’) is required for any 1.5 °C pathway, making this letter timely for the facilitative, or Talanoa, dialogue to be conducted by the UNFCCC in 2018. By highlighting the difference between net and gross reduction rates, often obscured in scenarios, we find that mid-term gross CO2 emission reduction rates in scenarios with CDR constraints increase to levels without historical precedence. This in turn highlights, in addition to the need to substantially increase CO2 reduction rates, the need to improve emission reductions for non-CO2 greenhouse gases. Further, scenarios in which all or part of the CDR is implemented as non-permanent storage exhibit storage loss emissions, which partly offset CDR, highlighting the importance of differentiating between net and gross CDR in scenarios. We find in some scenarios storage loss trending to similar values as gross CDR, indicating that gross CDR would have to be maintained simply to offset the storage losses of CO2 sequestered earlier, without any additional net climate benefit.

Efficient Hydrogen-Dependent Carbon Dioxide Reduction by Escherichia coli.

PubMed

Roger, Magali; Brown, Fraser; Gabrielli, William; Sargent, Frank

2018-01-08

Hydrogen-dependent reduction of carbon dioxide to formic acid offers a promising route to greenhouse gas sequestration, carbon abatement technologies, hydrogen transport and storage, and the sustainable generation of renewable chemical feedstocks [1]. The most common approach to performing direct hydrogenation of CO 2 to formate is to use chemical catalysts in homogeneous or heterogeneous reactions [2]. An alternative approach is to use the ability of living organisms to perform this reaction biologically. However, although CO 2 fixation pathways are widely distributed in nature, only a few enzymes have been described that have the ability to perform the direct hydrogenation of CO 2 [3-5]. The formate hydrogenlyase (FHL) enzyme from Escherichia coli normally oxidizes formic acid to carbon dioxide and couples that reaction directly to the reduction of protons to molecular hydrogen [6]. In this work, the reverse reaction of FHL is unlocked. It is established that FHL can operate as a highly efficient hydrogen-dependent carbon dioxide reductase when gaseous CO 2 and H 2 are placed under pressure (up to 10 bar). Using intact whole cells, the pressurized system was observed to rapidly convert 100% of gaseous CO 2 to formic acid, and >500 mM formate was observed to accumulate in solution. Harnessing the reverse reaction has the potential to allow the versatile E. coli system to be employed as an exciting new carbon capture technology or as a cell factory dedicated to formic acid production, which is a commodity in itself as well as a feedstock for the synthesis of other valued chemicals. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

ZnSe quantum dots modified with a Ni(cyclam) catalyst for efficient visible-light driven CO2 reduction in water.

PubMed

Kuehnel, Moritz F; Sahm, Constantin D; Neri, Gaia; Lee, Jonathan R; Orchard, Katherine L; Cowan, Alexander J; Reisner, Erwin

2018-03-07

A precious metal and Cd-free photocatalyst system for efficient CO 2 reduction in water is reported. The hybrid assembly consists of ligand-free ZnSe quantum dots (QDs) as a visible-light photosensitiser combined with a phosphonic acid-functionalised Ni(cyclam) catalyst, NiCycP. This precious metal-free photocatalyst system shows a high activity for aqueous CO 2 reduction to CO (Ni-based TON CO > 120), whereas an anchor-free catalyst, Ni(cyclam)Cl 2 , produced three times less CO. Additional ZnSe surface modification with 2-(dimethylamino)ethanethiol (MEDA) partially suppresses H 2 generation and enhances the CO production allowing for a Ni-based TON CO of > 280 and more than 33% selectivity for CO 2 reduction over H 2 evolution, after 20 h visible light irradiation ( λ > 400 nm, AM 1.5G, 1 sun). The external quantum efficiency of 3.4 ± 0.3% at 400 nm is comparable to state-of-the-art precious metal photocatalysts. Transient absorption spectroscopy showed that band-gap excitation of ZnSe QDs is followed by rapid hole scavenging and very fast electron trapping in ZnSe. The trapped electrons transfer to NiCycP on the ps timescale, explaining the high performance for photocatalytic CO 2 reduction. With this work we introduce ZnSe QDs as an inexpensive and efficient visible light-absorber for solar fuel generation.

Quantifying co-benefits of source-specific CO2 emission reductions in Canada and the US: An adjoint sensitivity analysis

NASA Astrophysics Data System (ADS)

Zhao, S.; Soltanzadeh, M.; Pappin, A. J.; Hakami, A.; Turner, M. D.; Capps, S.; Henze, D. K.; Percell, P.; Bash, J. O.; Napelenok, S. L.; Pinder, R. W.; Russell, A. G.; Nenes, A.; Baek, J.; Carmichael, G. R.; Stanier, C. O.; Chai, T.; Byun, D.; Fahey, K.; Resler, J.; Mashayekhi, R.

2016-12-01

Scenario-based studies evaluate air quality co-benefits by adopting collective measures introduced under a climate policy scenario cannot distinguish between benefits accrued from CO2 reductions among sources of different types and at different locations. Location and sector dependencies are important factors that can be captured in an adjoint-based analysis of CO2 reduction co-benefits. The present study aims to quantify how the ancillary benefits of reducing criteria co-pollutants vary spatially and by sector. The adjoint of USEPA's CMAQ was applied to quantify the health benefits associated with emission reduction of criteria pollutants (NOX) in on-road mobile, Electric Generation Units (EGUs), and other select sectors on a location-by-location basis across the US and Canada. These health benefits are then converted to CO2 emission reduction co-benefits by accounting for source-specific emission rates of criteria pollutants in comparison to CO2. We integrate the results from the adjoint of CMAQ with emission estimates from 2011 NEI at the county level, and point source data from EPA's Air Markets Program Data and National Pollutant Release Inventory (NPRI) for Canada. Our preliminary results show that the monetized health benefits (due to averted chronic mortality) associated with reductions of 1 ton of CO2 emissions is up to 65/ton in Canada and 200/ton in US for mobile on-road sector. For EGU sources, co-benefits are estimated at up to 100/ton and 10/ton for the US and Canada respectively. For Canada, the calculated co-benefits through gaseous pollutants including NOx is larger than those through PM2.5 due to the official association between NO2 exposure and chronic mortality. Calculated co-benefits show a great deal of spatial variability across emission locations for different sectors and sub-sectors. Implications of such spatial variability in devising control policy options that effectively address both climate and air quality objectives will be discussed.

Comparison of physically- and economically-based CO2-equivalences for methane

NASA Astrophysics Data System (ADS)

Boucher, O.

2012-05-01

There is a controversy on the role methane (and other short-lived species) should play in climate mitigation policies, and there is no consensus on what an optimal methane CO2-equivalence should be. We revisit this question by discussing some aspects of physically-based (i.e. global- warming potential or GWP and global temperature change potential or GTP) and socio-economically-based climate metrics. To this effect we use a simplified global damage potential (GDP) that was introduced by earlier authors and investigate the uncertainties in the methane CO2-equivalence that arise from physical and socio-economic factors. The median value of the methane GDP comes out very close to the widely used methane 100-yr GWP because of various compensating effects. However, there is a large spread in possible methane CO2-equivalences from this metric (1-99% interval: 10.0-42.5; 5-95% interval: 12.5-38.0) that is essentially due to the choice in some socio-economic parameters (i.e. the damage cost function and the discount rate). The main factor differentiating the methane 100-yr GTP from the methane 100-yr GWP and the GDP is the fact that the former metric is an end-point metric, whereas the latter are cumulative metrics. There is some rationale for an increase in the methane CO2-equivalence in the future as global warming unfolds, as implied by a convex damage function in the case of the GDP metric. We also show that a methane CO2-equivalence based on a pulse emission is sufficient to inform multi-year climate policies and emissions reductions, as long as there is enough visibility on CO2 prices and CO2-equivalences for the stakeholders.

Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies

DOE PAGES

Cao, Bingfei; Neuefeind, Joerg C.; Adzic, Radoslav R.; ...

2015-02-09

Monometallic (δ-MoN, Mo 5N 6, and Mo 2N) and bimetallic molybdenum nitrides (Co 0.6Mo 1.4N 2) were investigated as electrocatalysts for the oxygen reduction reaction (ORR), which is a key half-reaction in hydrogen fuel cells. Monometallic hexagonal molybdenum nitrides are found to exhibit improved activities over rock salt type molybdenum nitride (γ-Mo 2N), suggesting that improvements are due to either the higher molybdenum valence or a more favorable coordination environment in the hexagonal structures. Further enhancements in activity were found for hexagonal bimetallic cobalt molybdenum nitride (Co 0.6Mo 1.4N 2), resulting in a modest onset potential of 0.713 V versusmore » reversible hydrogen electrode (RHE). Co 0.6Mo 1.4N 2 exhibits good stability in acidic environments, and in the potential range lower than 0.5 V versus RHE, the ORR appears to proceed via a four-electron mechanism based on the analysis of rotating disc electrode results. A redetermination of the structures of the binary molybdenum nitrides was carried out using neutron diffraction data, which is far more sensitive to nitrogen site positions than X-ray diffraction data. In conclusion, the revised monometallic hexagonal nitride structures all share many common features with the Co 0.6Mo 1.4N 2 structure, which has alternating layers of cations in octahedral and trigonal prismatic coordination, and are thus not limited to only trigonal prismatic Mo environments (as was originally postulated for δ-MoN).« less

Nuclear Quantum Effects on Aqueous Electron Attachment and Redox Properties.

PubMed

Rybkin, Vladimir V; VandeVondele, Joost

2017-04-06

Nuclear quantum effects (NQEs) on the reduction and oxidation properties of small aqueous species (CO 2 , HO 2 , and O 2 ) are quantified and rationalized by first-principles molecular dynamics and thermodynamic integration. Vertical electron attachment, or electron affinity, and detachment energies (VEA and VDE) are strongly affected by NQEs, decreasing in absolute value by 0.3 eV going from a classical to a quantum description of the nuclei. The effect is attributed to NQEs that lessen the solvent response upon oxidation/reduction. The reduction of solvent reorganization energy is expected to be general for small solutes in water. In the thermodynamic integral that yields the free energy of oxidation/reduction, these large changes enter with opposite sign, and only a small net effect (0.1 eV) remains. This is not obvious for CO 2 , where the integrand is strongly influenced by NQEs due to the onset of interaction of the reduced orbital with the conduction band of the liquid during thermodynamic integration. We conclude that NQEs might not have to be included in the computation of redox potentials, unless high accuracy is needed, but are important for VEA and VDE calculations.

SrNb2O6 nanoplates as efficient photocatalysts for the preferential reduction of CO2 in the presence of H2O.

PubMed

Xie, Shunji; Wang, Yu; Zhang, Qinghong; Deng, Weiping; Wang, Ye

2015-02-25

We successfully synthesized SrNb2O6 with nanoplate morphology by a facile hydrothermal method. The SrNb2O6 nanoplate without any promoters or co-catalysts exhibited promising photocatalytic performance for the preferential reduction of CO2 with H2O vapour to CO and CH4 due to its high electron-hole separation and high CO2 chemisorption abilities.

Trade-based carbon sequestration accounting.

PubMed

King, Dennis M

2004-04-01

This article describes and illustrates an accounting method to assess and compare "early" carbon sequestration investments and trades on the basis of the number of standardized CO2 emission offset credits they will provide. The "gold standard" for such credits is assumed to be a relatively riskless credit based on a CO2 emission reduction that provides offsets against CO2 emissions on a one-for-one basis. The number of credits associated with carbon sequestration needs to account for time, risk, durability, permanence, additionality, and other factors that future trade regulators will most certainly use to assign "official" credits to sequestration projects. The method that is presented here uses established principles of natural resource accounting and conventional rules of asset valuation to "score" projects. A review of 20 "early" voluntary United States based CO2 offset trades that involve carbon sequestration reveals that the assumptions that buyers, sellers, brokers, and traders are using to characterize the economic potential of their investments and trades vary enormously. The article develops a "universal carbon sequestration credit scoring equation" and uses two of these trades to illustrate the sensitivity of trade outcomes to various assumptions about how future trade auditors are likely to "score" carbon sequestration projects in terms of their "equivalency" with CO2 emission reductions. The article emphasizes the importance of using a standard credit scoring method that accounts for time and risk to assess and compare even unofficial prototype carbon sequestration trades. The scoring method illustrated in this article is a tool that can protect the integrity of carbon sequestration credit trading and can assist buyers and sellers in evaluating the real economic potential of prospective trades.

Coupled ferredoxin and crotonyl coenzyme A (CoA) reduction with NADH catalyzed by the butyryl-CoA dehydrogenase/Etf complex from Clostridium kluyveri.

PubMed

Li, Fuli; Hinderberger, Julia; Seedorf, Henning; Zhang, Jin; Buckel, Wolfgang; Thauer, Rudolf K

2008-02-01

Cell extracts of butyrate-forming clostridia have been shown to catalyze acetyl-coenzyme A (acetyl-CoA)- and ferredoxin-dependent formation of H2 from NADH. It has been proposed that these bacteria contain an NADH:ferredoxin oxidoreductase which is allosterically regulated by acetyl-CoA. We report here that ferredoxin reduction with NADH in cell extracts from Clostridium kluyveri is catalyzed by the butyryl-CoA dehydrogenase/Etf complex and that the acetyl-CoA dependence previously observed is due to the fact that the cell extracts catalyze the reduction of acetyl-CoA with NADH via crotonyl-CoA to butyryl-CoA. The cytoplasmic butyryl-CoA dehydrogenase complex was purified and is shown to couple the endergonic reduction of ferredoxin (E0' = -410 mV) with NADH (E0' = -320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (E0' = -10 mV) with NADH. The stoichiometry of the fully coupled reaction is extrapolated to be as follows: 2 NADH + 1 oxidized ferredoxin + 1 crotonyl-CoA = 2 NAD+ + 1 ferredoxin reduced by two electrons + 1 butyryl-CoA. The implications of this finding for the energy metabolism of butyrate-forming anaerobes are discussed in the accompanying paper.

Impact of naturally leaking carbon dioxide on soil properties and ecosystems in the Qinghai-Tibet plateau

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

Zhao, Xiaohong; Deng, Hongzhang; Wang, Wenke

One of the major concerns for CO 2 capture and storage (CCS) is the potential risk of CO 2 leakage from storage reservoirs on the shallow soil property and vegetation. This study utilizes a naturally occurring CO 2 leaking site in the Qinghai-Tibet Plateau to analog a “leaking CCS site”. Our observations from this site indicates that long-term CO 2 invasion in the vadose zone results in variations of soil properties, such as pH fluctuation, slight drop of total organic carbon, reduction of nitrogen and phosphorus, and concentration changes of soluble ions. Simultaneously, XRD patterns of the soil suggest thatmore » crystallization of soil is enhanced and mineral contents of calcite and anorthite in soil are increased substantially. Parts of the whole ecosystem such as natural wild plants, soil dwelling animals and microorganisms in shallow soil are affected as well. Under a moderate CO 2 concentration (less than 110000 ppm), wild plant growth and development are improved, while an intensive CO2 flux over 112000 ppm causes adverse effects on the plant growth, physiological and biochemical system of plants, and crop quality of wheat. Results of this study provide valuable insight for understanding the possible environmental impacts associated with potential CO 2 leakage into shallow sediments at carbon sequestration sites.« less

Impact of naturally leaking carbon dioxide on soil properties and ecosystems in the Qinghai-Tibet plateau

DOE PAGES

Zhao, Xiaohong; Deng, Hongzhang; Wang, Wenke; ...

2017-06-07

One of the major concerns for CO 2 capture and storage (CCS) is the potential risk of CO 2 leakage from storage reservoirs on the shallow soil property and vegetation. This study utilizes a naturally occurring CO 2 leaking site in the Qinghai-Tibet Plateau to analog a “leaking CCS site”. Our observations from this site indicates that long-term CO 2 invasion in the vadose zone results in variations of soil properties, such as pH fluctuation, slight drop of total organic carbon, reduction of nitrogen and phosphorus, and concentration changes of soluble ions. Simultaneously, XRD patterns of the soil suggest thatmore » crystallization of soil is enhanced and mineral contents of calcite and anorthite in soil are increased substantially. Parts of the whole ecosystem such as natural wild plants, soil dwelling animals and microorganisms in shallow soil are affected as well. Under a moderate CO 2 concentration (less than 110000 ppm), wild plant growth and development are improved, while an intensive CO2 flux over 112000 ppm causes adverse effects on the plant growth, physiological and biochemical system of plants, and crop quality of wheat. Results of this study provide valuable insight for understanding the possible environmental impacts associated with potential CO 2 leakage into shallow sediments at carbon sequestration sites.« less

Assessing potential impacts of phosphate precipitation on nitrous oxide emissions and the carbon footprint of wastewater treatment plants.

PubMed

Kosse, Pascal; Lübken, Manfred; Schmidt, Torsten C; Lange, Ruben-Laurids; Wichern, Marc

2018-02-15

Metal salts are widely used for the precipitation of phosphorus during wastewater treatment transforming soluble orthophosphate to an insoluble salt. In practice, more complex reactions are taking place including a reduction of the chemical solubility of dissolved greenhouse gases, such as nitrous oxide, present in the wastewater stream. In this respect, it was postulated that phosphorous precipitation will lead to artificial N 2 O stripping and hence to an increased carbon footprint of wastewater treatment plants. From lab-scale experiments utilizing N 2 O-saturated synthetic sewage solutions, it was evidenced that metal salt addition leads to N 2 O stripping with 20.8 g N 2 O per liter for a FeCl 2 -based precipitant to 26.4 g N 2 O per liter for a Al n (OH) m Cl3 n-m -based precipitant. Taking this maximum potential stripping effect into account for a carbon footprint analysis, a potential contribution of 16.11 kg CO 2,eq ·PE -1 ·a -1 was calculated in a case study, where FeCl 3 was considered. With respect to the defined system boundary conditions, the overall on-site and off-site CO 2 emissions were raised by 34% from 46.87 kg CO 2,eq ·PE -1 ·a -1 to 62.97 kg CO 2,eq ·PE -1 ·a -1 through CO 2,eq coming from phosphorous precipitation.

Canopy warming caused photosynthetic acclimation and reduced seed yield in maize grown at ambient and elevated [CO2 ].

PubMed

Ruiz-Vera, Ursula M; Siebers, Matthew H; Drag, David W; Ort, Donald R; Bernacchi, Carl J

2015-11-01

Rising atmospheric CO2 concentration ([CO2 ]) and attendant increases in growing season temperature are expected to be the most important global change factors impacting production agriculture. Although maize is the most highly produced crop worldwide, few studies have evaluated the interactive effects of elevated [CO2 ] and temperature on its photosynthetic physiology, agronomic traits or biomass, and seed yield under open field conditions. This study investigates the effects of rising [CO2 ] and warmer temperature, independently and in combination, on maize grown in the field throughout a full growing season. Free-air CO2 enrichment (FACE) technology was used to target atmospheric [CO2 ] to 200 μmol mol(-1) above ambient [CO2 ] and infrared heaters to target a plant canopy increase of 3.5 °C, with actual season mean heating of ~2.7 °C, mimicking conditions predicted by the second half of this century. Photosynthetic gas-exchange parameters, leaf nitrogen and carbon content, leaf water potential components, and developmental measurements were collected throughout the season, and biomass and yield were measured at the end of the growing season. As predicted for a C4 plant, elevated [CO2 ] did not stimulate photosynthesis, biomass, or yield. Canopy warming caused a large shift in aboveground allocation by stimulating season-long vegetative biomass and decreasing reproductive biomass accumulation at both CO2 concentrations, resulting in decreased harvest index. Warming caused a reduction in photosynthesis due to down-regulation of photosynthetic biochemical parameters and the decrease in the electron transport rate. The reduction in seed yield with warming was driven by reduced photosynthetic capacity and by a shift in aboveground carbon allocation away from reproduction. This field study portends that future warming will reduce yield in maize, and this will not be mitigated by higher atmospheric [CO2 ] unless appropriate adaptation traits can be introduced into future cultivars. © 2015 John Wiley & Sons Ltd.

Prescribed fire as a means of reducing forest carbon emissions in the western United States.

PubMed

Wiedinmyer, Christine; Hurteau, Matthew D

2010-03-15

Carbon sequestration by forested ecosystems offers a potential climate change mitigation benefit. However, wildfire has the potential to reverse this benefit In the western United States, climate change and land management practices have led to increases in wildfire intensity and size. One potential means of reducing carbon emissions from wildfire is the use of prescribed burning,which consumes less biomass and therefore releases less carbon to the atmosphere. This study uses a regional fire emissions model to estimate the potential reduction in fire emissions when prescribed burning is applied in dry, temperate forested systems of the western U.S. Daily carbon dioxide (CO(2)) fire emissions for 2001-2008 were calculated for the western U.S. for two cases: a default wildfire case and one in which prescribed burning was applied. Wide-scale prescribed fire application can reduce CO(2) fire emissions for the western U.S. by 18-25%1 in the western U.S., and by as much as 60% in specific forest systems. Although this work does not address important considerations such as the feasibility of implementing wide-scale prescribed fire management or the cumulative emissions from repeated prescribed burning, it does provide constraints on potential carbon emission reductions when prescribed burning is used.

Iron Reduction and Carbonate Precipitation by Shewanella oneidensis

NASA Astrophysics Data System (ADS)

Zeng, Z.; Tice, M. M.

2011-12-01

This study is to contribute to better understanding of how Archean microbes induced carbonate diagenesis in mats and stromatolites. Previous studies showed sulfate reduction, a common promoter of carbonate precipitation in modern mats[1], is likely to have been less effective in Archean mats in marine fluids lower in sulfate[2]. Alternatively, iron reduction produces far more alkalinity per unit carbon respired than sulfate reduction. Therefore, we hypothesize iron reduction can promote much more carbonate precipitation than sulfate reduction. Our study might also have some relevance to banded iron formation on which microbial iron reduction played a potential role[3]. To test our hypothesis, Shewanella oneidensis MR-1, a dissimilatory iron reducing bacterium will be cultured anaerobically (79%N2, 20%CO2 and 1%H2) in basal medium to trigger iron reduction. Lactate will be used as electron donor, and the electron acceptor will be fresh ferrihydrite. Culture medium will be added with various metal ions, such as Ca2+ and Mg2+, to obtain potential carbonate precipitate. Escherichia coli (with fumarate added as an electron acceptor) will be used to provide a comparison to live but non-iron- reduction cells. After 20 days incubation, precipitate will be collected, washed and identified by X-ray diffraction (XRD). Besides, iron reduction rate (ferrozine assay)[4], PH and amount of precipitate (carbonate and oxidize fractions)[5] will be measured over time to well understand how S. oneidensis drives carbonate precipitation.

40 CFR 86.1869-12 - CO2 credits for off-cycle CO2-reducing technologies.

Code of Federal Regulations, 2013 CFR

2013-07-01

... where the CO2 reduction benefit of the technology is not adequately captured on the Federal Test Procedure and/or the Highway Fuel Economy Test. These technologies must have a measurable, demonstrable, and verifiable real-world CO2 reduction that occurs outside the conditions of the Federal Test Procedure and the...

Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

NASA Astrophysics Data System (ADS)

Yang, Hong Bin; Hung, Sung-Fu; Liu, Song; Yuan, Kaidi; Miao, Shu; Zhang, Liping; Huang, Xiang; Wang, Hsin-Yi; Cai, Weizheng; Chen, Rong; Gao, Jiajian; Yang, Xiaofeng; Chen, Wei; Huang, Yanqiang; Chen, Hao Ming; Li, Chang Ming; Zhang, Tao; Liu, Bin

2018-02-01

Electrochemical reduction of CO2 to chemical fuel offers a promising strategy for managing the global carbon balance, but presents challenges for chemistry due to the lack of effective electrocatalyst. Here we report atomically dispersed nickel on nitrogenated graphene as an efficient and durable electrocatalyst for CO2 reduction. Based on operando X-ray absorption and photoelectron spectroscopy measurements, the monovalent Ni(i) atomic center with a d9 electronic configuration was identified as the catalytically active site. The single-Ni-atom catalyst exhibits high intrinsic CO2 reduction activity, reaching a specific current of 350 A gcatalyst-1 and turnover frequency of 14,800 h-1 at a mild overpotential of 0.61 V for CO conversion with 97% Faradaic efficiency. The catalyst maintained 98% of its initial activity after 100 h of continuous reaction at CO formation current densities as high as 22 mA cm-2.

Unexpected effect of catalyst concentration on photochemical CO2 reduction by trans(Cl)–Ru(bpy)(CO)2Cl2: new mechanistic insight into the CO/HCOO– selectivity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc00199d Click here for additional data file.

PubMed Central

Kuramochi, Yusuke; Itabashi, Jun; Fukaya, Kyohei; Enomoto, Akito; Yoshida, Makoto

2015-01-01

Photochemical CO2 reduction catalysed by trans(Cl)–Ru(bpy)(CO)2Cl2 (bpy = 2,2′-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO–) in N,N-dimethylacetamide (DMA)/water containing [Ru(bpy)3]2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO–) in the photochemical CO2 reduction: the ratio of CO/HCOO– decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO– is selectively produced by the formation of a Ru(i)–Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru–Ru bond dissociates in the reaction of the dimer with CO2, and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO–. The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO– in the photochemical CO2 reduction catalysed by [Ru(bpy)(CO)2Cl]2 (0.05 mM) are very similar to those of the reduction catalysed by trans(Cl)–Ru(bpy)(CO)2Cl2 (0.10 mM), and that HCOO– formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO2 reduction using [Ru(4dmbpy)3]2+ (4dmbpy = 4,4′-dimethyl-2,2′-bipyridine) instead of [Ru(bpy)3]2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy)3]2+ by BNAH than that of excited [Ru(bpy)3]2+. We have further synthesized trans(Cl)–Ru(6Mes-bpy)(CO)2Cl2 (6Mes-bpy = 6,6′-dimesityl-2,2′-bipyridine), which bears bulky substituents at the 6,6′-positions in the 2,2′-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the steric hindrance. We have found that this ruthenium complex selectively produces CO, which strongly supports the catalytic mechanism proposed in this work. PMID:28706681

Ultra-Low Carbon Emissions from Coal-Fired Power Plants through Bio-Oil Co-Firing and Biochar Sequestration.

PubMed

Dang, Qi; Mba Wright, Mark; Brown, Robert C

2015-12-15

This study investigates a novel strategy of reducing carbon emissions from coal-fired power plants through co-firing bio-oil and sequestering biochar in agricultural lands. The heavy end fraction of bio-oil recovered from corn stover fast pyrolysis is blended and co-fired with bituminous coal to form a bio-oil co-firing fuel (BCF). Life-cycle greenhouse gas (GHG) emissions per kWh electricity produced vary from 1.02 to 0.26 kg CO2-eq among different cases, with BCF heavy end fractions ranging from 10% to 60%, which corresponds to a GHG emissions reduction of 2.9% to 74.9% compared with that from traditional bituminous coal power plants. We found a heavy end fraction between 34.8% and 37.3% is required to meet the Clean Power Plan's emission regulation for new coal-fired power plants. The minimum electricity selling prices are predicted to increase from 8.8 to 14.9 cents/kWh, with heavy end fractions ranging from 30% to 60%. A minimum carbon price of $67.4 ± 13 per metric ton of CO2-eq was estimated to make BCF power commercially viable for the base case. These results suggest that BCF co-firing is an attractive pathway for clean power generation in existing power plants with a potential for significant reductions in carbon emissions.

Structure and reactivity of ferrihydrite-soil organic carbon-calcium ternary complexes

NASA Astrophysics Data System (ADS)

Yang, Y.; Adhikari, D.; Sowers, T.; Stuckey, J.; Poulson, S.; Sparks, D. L.

2017-12-01

Complete understanding about the interactions between soil organic carbon (SOC) and minerals is important for predicting the stability of SOC and its response to climate change. Recent studies have shown the importance of calcium (Ca)-bearing minerals and iron (Fe) oxide in associating with and stabilizing SOC. In this study, we have investigated the formation and reactivity of ferrihydrite-SOC-Ca ternary complexes. During the co-precipitation of ferrihydrite with SOC in the presence of Ca2+, 60% of SOC can be co-precipitated with ferrihydrite at a C/Fe (molar ratio) of up to 10, whereas the Ca/Fe ratio was saturated at 0.2. Increasing amount of Ca2+ did not affect the co-precipitation of SOC with ferrihydrite or the lability of ferrihydrite-bound SOC. In addition, microbial reduction of ferrihydrite and reductive release of ferrihydrite-bound SOC were not influenced by the presence of Ca, but the pathway for Fe mineral transformation during the reduction was affected by Ca. In the meantime, Fe reduction selectively released carboxylic-enriched SOC. As a comparison, the presence of SOC increased the incorporation of Ca into the structure of ferrihydrite. Our results indicate the formation of ferrihydrite-SOC-Ca complexes, with organic carbon bridging the ferrihydrite and Ca. Such ternary complexes potentially play an important role in regulating the interactions between SOC and mineral phases in soil.

Physicochemical properties of metal-doped activated carbons and relationship with their performance in the removal of SO2 and NO.

PubMed

Gao, Xiang; Liu, Shaojun; Zhang, Yang; Luo, Zhongyang; Cen, Kefa

2011-04-15

Several metal-doped activated carbons (Fe, Co, Ni, V, Mn, Cu and Ce) were prepared and characterized. The results of N(2) adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy indicated that some metals (Cu and Fe) were partly reduced by carbon during preparation. Activity tests for the removal of SO(2) and the selective catalytic reduction of NO with ammonia were carried out. Due to different physicochemical properties, different pathways for the SO(2) removal had been put out, i.e., catalytic oxidation, direct reaction and adsorption. This classification depended on the standard reduction potentials of metal redox pairs. Samples impregnated with V, Ce and Cu showed good activity for NO reduction by NH(3), which was also ascribed to the reduction potential values of metal redox pairs. Ce seemed to be a promising alternative to V due to the higher activity in NO reduction and the nontoxic property. A metal cation which could easily convert between the two valences seemed to be crucial to the good performance of both SO(2) and NO removal, just like V and Cu. Copyright © 2011 Elsevier B.V. All rights reserved.

Activation of CO2 by supported Cu clusters.

PubMed

Iyemperumal, Satish Kumar; Deskins, N Aaron

2017-11-01

Catalytic reduction of carbon dioxide to useful chemicals is a potent way to mitigate this greenhouse gas, but the challenge lies in finding active reduction catalysts. Using density functional theory we studied CO 2 activation over TiO 2 -supported Cu clusters of size 1-4 atoms. The linear to bent transformation of CO 2 is necessary for activation, and we found that all the clusters stabilized bent CO 2 , along with a significant gain of electrons on the CO 2 (indicative of activation). On all the TiO 2 supported Cu clusters, the interfacial sites were found to stabilize the bent CO 2 adsorption, where the active site of adsorption on Cu dimer, trimer and tetramer was on the Cu atom farthest away from the TiO 2 surface. Particularly, the Cu dimer stabilized bent CO 2 very strongly, although this species was found to be unstable on the surface. A synthesis technique that could stabilize the Cu dimer could therefore lead to a very active catalyst. Furthermore we found (using vibrational and charge analysis) that the active sites for the CO 2 activation predominantly had 0 and +1 oxidation states; the oxidation state of Cu is known to directly affect CO 2 reduction activity. Our study shows TiO 2 -supported small Cu clusters can be active catalysts for CO 2 reduction and also provides further motivation for theoretical and experimental studies of metal clusters.

Combined In-Situ XRD and In-Situ XANES Studies on the Reduction Behavior of a Rhenium Promoted Cobalt Catalyst

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

Kumar, Nitin; Payzant, E Andrew; Jothimurugesan, K

2011-01-01

A 10% Co 4% Re/(2% Zr/SiO2) catalyst was prepared by co-impregnation using a silica support modified by 2% Zr. The catalyst was characterized by temperature programmed reduction (TPR), in situ XRD and in situ XANES analysis where it was simultaneously exposed to H2 using a temperature programmed ramp. The results showed the two step reduction of large crystalline Co3O4 with CoO as an intermediate. TPR results showed that the reduction of highly dispersed Co3O4 was facilitated by reduced rhenium by a H2-spillover mechanism. In situ XRD results showed the presence of both, Co-hcp and Co-fcc phases in the reduced catalystmore » at 400 C. However, the Co-hcp phase was more abundant, which is thought to be the more active phase as compared to the Co-fcc phase for CO hydrogenation. CO hydrogenation at 270 C and 5 bar pressure produces no detectable change in the phases during the time of experiment. In situ XANES results showed a decrease in the metallic cobalt in the presence of H2/CO, which can be attributed due to oxidation of the catalyst by reaction under these conditions.« less

Direct Observation by Rapid-Scan FT-IR Spectroscopy of Two-Electron-Reduced Intermediate of Tetraaza Catalyst [Co IIN 4H(MeCN)] 2+ Converting CO 2 to CO

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

Sheng, Hua; Frei, Heinz

In the search for the two-electron-reduced intermediate of the tetraaza catalyst [Co IIN 4H(MeCN)] 2+ (N 4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene) for CO 2 reduction and elementary steps that result in the formation of CO product, rapid-scan FT-IR spectroscopy of the visible-light-sensitized catalysis, using Ir(ppy) 3 in wet acetonitrile (CD 3CN) solution, led to the observation of two sequential intermediates. The initially formed one-electron-reduced [Co IN 4H] +--CO 2 adduct was converted by the second electron to a transient [Co IN 4H] +--CO 2 - complex that spontaneously converted CO 2 to CO in a rate-limiting step on the second time scalemore » in the dark under regeneration of the catalyst (room temperature). The macrocycle IR spectra of the [Co IN 4H] +--CO 2 - complex and the preceding one-electron [Co IN 4H] +--CO 2 intermediate show close similarity but distinct differences in the carboxylate modes, indicating that the second electron resides mainly on the CO 2 ligand. Vibrational assignments are corroborated by 13C isotopic labeling. The structure and stability of the two-electron-reduced intermediate derived from the time-resolved IR study are in good agreement with recent predictions by DFT electronic structure calculations. This is the first observation of an intermediate of a molecular catalyst for CO 2 reduction during the bond-breaking step producing CO. The reaction pathway for the Co tetraaza catalyst uncovered here suggests that the competition between CO 2 reduction and proton reduction of a macrocyclic multi-electron catalyst is steered toward CO 2 activation if the second electron is directly captured by an adduct of CO 2 and the one-electron-reduced catalyst intermediate.« less

Methodology for Examining Potential Technology Breakthroughs for Mitigating CO2 and Application to Centralized Solar Photovoltaics

EPA Science Inventory

Aggressive reductions in US greenhouse gas emissions will require radical changes in how society generates and uses energy. Technological breakthroughs will be necessary if we are to make this transition cost effectively. With limited resources, understanding the breakthrough pot...

Free energy landscape of electrocatalytic CO2 reduction to CO on aqueous FeN4 center embedded graphene studied by ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sheng, Tian; Sun, Shi-Gang

2017-11-01

Experiments have found that the porphyrin-like FeN4 site in Fe-N-C materials is highly efficient for the electrochemical reduction of CO2 into CO. In this work, we investigated the reduction mechanisms on FeN4 embedded graphene layer catalyst with some explicit water molecules by combining the constrained ab initio molecular dynamics simulations and thermodynamic integrations. The reaction free energy and electron transfer in each elementary step were identified. The initial CO2 activation was identified to go through the first electron transfer to form adsorbed CO2- anion and the CO desorption was the rate limiting step in the overall catalytic cycle.

Photocatalytic Conversion of CO2 to CO by a Copper(II) Quaterpyridine Complex.

PubMed

Guo, Zhenguo; Yu, Fei; Yang, Ying; Leung, Chi-Fai; Ng, Siu-Mui; Ko, Chi-Chiu; Cometto, Claudio; Lau, Tai-Chu; Robert, Marc

2017-10-23

The invention of efficient systems for the photocatalytic reduction of CO 2 comprising earth-abundant metal catalysts is a promising approach for the production of solar fuels. One bottleneck is to design highly selective and robust molecular complexes that are able to transform the CO 2 gas. The Cu II quaterpyridine complex [Cu(qpy)] 2+ (1) is found to be a highly efficient and selective catalyst for visible-light driven CO 2 reduction in CH 3 CN using [Ru(bpy) 3 ] 2+ (bpy: bipyridine) as photosensitizer and BIH/TEOA (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole/triethanolamine) as sacrificial reductant. The photocatalytic reaction is greatly enhanced by the presence of H 2 O (1-4 % v/v), and a turnover number of >12 400 for CO production can be achieved with 97 % selectivity, which is among the highest of molecular 3d CO 2 reduction catalysts. Results from Hg poisoning and dynamic light scattering experiments suggest that this photocatalyst is homogenous. To the best of our knowledge, 1 is the first example of molecular Cu-based catalyst for the photoreduction of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Does consideration of GHG reductions change local decision making? A Case Study in Chile

NASA Astrophysics Data System (ADS)

Cifuentes, L. A.; Blumel, G.

2003-12-01

While local air pollution has been a public concern in developing countries for some time, climate change is looked upon as a non-urgent, developed world problem. In this work we present a case study of the interaction of measures to abate air pollution and measures to mitigate GHG emissions in Santiago, Chile, with the purpose of determining if the consideration of reductions in GHG affects the decisions taken to mitigate local air pollution. The emissions reductions of both GHG and local air pollutants were estimated from emission factors (some derived locally) and changes in activity levels. Health benefits due to air pollution abatement were computed using figures derived previously for the cost benefit analysis of Santiago's Decontamination Plan, transferred to the different cities taking into consideration local demographic and income data. The Santiago estimates were obtained using the damage function approach, based on some local epidemiological studies, and on local health and demographic data. Unit social values for the effects were estimated locally (for cost of treatment and lost productivity values) or extrapolated from US values (mainly for WTP values) using the ratio of per-capita income and an income elasticity of 1. The average benefits of emission abatement (in 1997 US\\ per ton) are 1,800 (1,200-2300) for NOx, 3,000 (2,100-3900) for SO2, 31,900 (21,900 - 41,900) for PM, and 630 (430 - 830) for resuspended dust. Economic benefits due to carbon reduction were considered at 3.5, 10 and 20 UStCO2. Marginal abatement cost curves were constructed considering private and net costs (private less the potential sales of carbon credits) Due to the bottom-up approach to constructing the marginal cost curve, many abatement measures (like congestion tolls and CNG instead of diesel buses) amounting to 8% reduction of PM2.5 concentration, exhibit a negative private cost. If the health benefits are considered for the decision, a maximum reduction of 22% in PM2.5 levels is obtained. Although many measures have associated reductions in GHG, due to the relatively low price considered for carbon reductions, when the potential benefits of CO2 sales are considered, this number does not increases. Therefore, consideration of the CO2 benefits did not change the decision for any of the 36 measures analyzed. This confirms that the main driver for air pollution policy is likely to continue to be local concerns, like public health issues.

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

Duan, Lele; Manbeck, Gerald F.; Kowalczyk, Marta

Ruthenium complexes with proton-responsive ligands [Ru(tpy)(nDHBP)(NCCH 3)](CF 3SO 3) 2 (tpy = 2,2':6',2"-terpyridine; nDHBP = n,n'-dihydroxy-2,2'-bipyridine, n = 4 or 6) were examined in this study for reductive chemistry and as catalysts for CO 2 reduction. Electrochemical reduction of [Ru(tpy)(nDHBP)(NCCH 3)] 2+ generates deprotonated species through interligand electron transfer in which the initially formed tpy radical anion reacts with a proton source to produce singly and doubly deprotonated complexes that are identical to those obtained by base titration. A third reduction (i.e., reduction of [Ru(tpy)(nDHBP–2H +)] 0) triggers catalysis of CO 2 reduction; however, the catalytic efficiency is strikingly lowermore » than that of unsubstituted [Ru(tpy)(bpy)(NCCH 3)] 2+ (bpy = 2,2'-bipyridine). Cyclic voltammetry, bulk electrolysis, and spectroelectrochemical infrared experiments suggest the reactivity of CO 2 at both the Ru center and the deprotonated quinone-type ligand. Lastly, the Ru carbonyl formed by the intermediacy of a metallocarboxylic acid is stable against reduction, and mass spectrometry analysis of this product indicates the presence of two carbonates formed by the reaction of DHBP–2H + with CO 2.« less

Electrochemical Reduction of Carbon Dioxide to Methanol by Direct Injection of Electrons into Immobilized Enzymes on a Modified Electrode.

PubMed

Schlager, Stefanie; Dumitru, Liviu Mihai; Haberbauer, Marianne; Fuchsbauer, Anita; Neugebauer, Helmut; Hiemetsberger, Daniela; Wagner, Annika; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

2016-03-21

We present results for direct bio-electrocatalytic reduction of CO2 to C1 products using electrodes with immobilized enzymes. Enzymatic reduction reactions are well known from biological systems where CO2 is selectively reduced to formate, formaldehyde, or methanol at room temperature and ambient pressure. In the past, the use of such enzymatic reductions for CO2 was limited due to the necessity of a sacrificial co-enzyme, such as nicotinamide adenine dinucleotide (NADH), to supply electrons and the hydrogen equivalent. The method reported here in this paper operates without the co-enzyme NADH by directly injecting electrons from electrodes into immobilized enzymes. We demonstrate the immobilization of formate, formaldehyde, and alcohol dehydrogenases on one-and-the-same electrode for direct CO2 reduction. Carbon felt is used as working electrode material. An alginate-silicate hybrid gel matrix is used for the immobilization of the enzymes on the electrode. Generation of methanol is observed for the six-electron reduction with Faradaic efficiencies of around 10%. This method of immobilization of enzymes on electrodes offers the opportunity for electrochemical application of enzymatic electrodes to many reactions in which a substitution of the expensive sacrificial co-enzyme NADH is desired. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soil respiration contributes substantially to urban carbon fluxes in the greater Boston area.

PubMed

Decina, Stephen M; Hutyra, Lucy R; Gately, Conor K; Getson, Jackie M; Reinmann, Andrew B; Short Gianotti, Anne G; Templer, Pamela H

2016-05-01

Urban areas are the dominant source of U.S. fossil fuel carbon dioxide (FFCO2) emissions. In the absence of binding international treaties or decisive U.S. federal policy for greenhouse gas regulation, cities have also become leaders in greenhouse gas reduction efforts through climate action plans. These plans focus on anthropogenic carbon flows only, however, ignoring a potentially substantial contribution to atmospheric carbon dioxide (CO2) concentrations from biological respiration. Our aim was to measure the contribution of CO2 efflux from soil respiration to atmospheric CO2 fluxes using an automated CO2 efflux system and to use these measurements to model urban soil CO2 efflux across an urban area. We find that growing season soil respiration is dramatically enhanced in urban areas and represents levels of CO2 efflux of up to 72% of FFCO2 within greater Boston's residential areas, and that soils in urban forests, lawns, and landscaped cover types emit 2.62 ± 0.15, 4.49 ± 0.14, and 6.73 ± 0.26 μmolCO2 m(-2) s(-1), respectively, during the growing season. These rates represent up to 2.2 times greater soil respiration than rates found in nearby rural ecosystems in central Massachusetts (MA), a potential consequence of imported carbon amendments, such as mulch, within a general regime of landowner management. As the scientific community moves rapidly towards monitoring, reporting, and verification of CO2 emissions using ground based approaches and remotely-sensed observations to measure CO2 concentrations, our results show that measurement and modeling of biogenic urban CO2 fluxes will be a critical component for verification of urban climate action plans. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

A combination of CoO and Co nanoparticles supported on electrospun carbon nanofibers as highly stable air electrodes

NASA Astrophysics Data System (ADS)

Alegre, Cinthia; Busacca, Concetta; Di Blasi, Orazio; Antonucci, Vincenzo; Aricò, Antonino Salvatore; Di Blasi, Alessandra; Baglio, Vincenzo

2017-10-01

Bifunctional materials able to catalyze both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions in alkaline media are still a challenge for the progress of energy conversion and storage devices such as metal-air batteries or unitized regenerative fuel cells. In this work, carbon nanofibers synthesized by electrospinning are modified with a combination of cobalt oxide and metallic cobalt (CoO-Co/CNF) and studied as a bifunctional air electrode for metal-air batteries. The performance of CoO-Co/CNF for both reactions is compared with state-of-the-art catalysts such as Pt/C and IrO2. The combination of cobalt oxide and metallic cobalt, finely distributed on the surface of graphitic carbon nanofibers, leads to a bifunctional catalyst with a half-wave potential for the ORR slightly better than Pt/C and a reversibility (ΔEOER-ORR) of 809 mV. The stability of CoO-Co/CNF is assessed by means of different stress tests: polarizations at high electrochemical potentials (2 V vs. RHE), rapid charge-discharge cycles at ±80 mA cm-2 and long durability tests by charging for 12 h at 60 mA cm-2 and discharging for 8 h at -80 mA cm-2. CoO-Co/CNF shows a remarkable stability, maintaining, at least, an 82% of its performance for the ORR after the stress tests, even when cycled for more than 100 h.

Simulated Effect of Carbon Cycle Feedback on Climate Response to Solar Geoengineering

NASA Astrophysics Data System (ADS)

Cao, Long; Jiang, Jiu

2017-12-01

Most modeling studies investigate climate effects of solar geoengineering under prescribed atmospheric CO2, thereby neglecting potential climate feedbacks from the carbon cycle. Here we use an Earth system model to investigate interactive feedbacks between solar geoengineering, global carbon cycle, and climate change. We design idealized sunshade geoengineering simulations to prevent global warming from exceeding 2°C above preindustrial under a CO2 emission scenario with emission mitigation starting from middle of century. By year 2100, solar geoengineering reduces the burden of atmospheric CO2 by 47 PgC with enhanced carbon storage in the terrestrial biosphere. As a result of reduced atmospheric CO2, consideration of the carbon cycle feedback reduces required insolation reduction in 2100 from 2.0 to 1.7 W m-2. With higher climate sensitivity the effect from carbon cycle feedback becomes more important. Our study demonstrates the importance of carbon cycle feedback in climate response to solar geoengineering.

Comparison of physically- and economically-based CO2-equivalences for methane

NASA Astrophysics Data System (ADS)

Boucher, O.

2012-01-01

There is a controversy on the role methane (and other short-lived species) should play in climate mitigation policies and no consensus on what an optimal methane CO2-equivalence should be. We revisit this question by discussing the relative merits of physically-based (i.e. Global Warming Potential or GWP and Global Temperature change Potential or GTP) and socio-economically-based climate metrics. To this effect we use a simplified Global Damage Potential (GDP) that was introduced by earlier authors and investigate the uncertainties in the methane CO2-equivalence that arise from physical and socio-economic factors. The median value of the methane GDP comes out very close to the widely used methane 100-year GWP because of various compensating effects. However there is a large spread in possible methane CO2-equivalences (1-99% interval: 10.0-42.5; 5-95% interval: 12.5-38.0) that is essentially due to the choice in some socio-economic parameters (i.e. the damage cost function and the discount rate). The methane 100-year GTP falls outside these ranges. It is legitimate to increase the methane CO2-equivalence in the future as global warming unfolds. While changes in biogeochemical cycles and radiative efficiencies cause some small changes to physically-based metrics, a systematic increase in the methane CO2-equivalence can only be achieved by some ad-hoc shortening of the time horizon. In contrast using a convex damage cost function provides a natural increase in the methane CO2-equivalence for the socio-economically-based metrics. We also show that a methane CO2-equivalence based on a pulse emission is sufficient to inform multi-year climate policies and emissions reductions as long as there is some degree of visibility on CO2 prices and CO2-equivalences.

Leaf-architectured 3D Hierarchical Artificial Photosynthetic System of Perovskite Titanates Towards CO2 Photoreduction Into Hydrocarbon Fuels

PubMed Central

Zhou, Han; Guo, Jianjun; Li, Peng; Fan, Tongxiang; Zhang, Di; Ye, Jinhua

2013-01-01

The development of an “artificial photosynthetic system” (APS) having both the analogous important structural elements and reaction features of photosynthesis to achieve solar-driven water splitting and CO2 reduction is highly challenging. Here, we demonstrate a design strategy for a promising 3D APS architecture as an efficient mass flow/light harvesting network relying on the morphological replacement of a concept prototype-leaf's 3D architecture into perovskite titanates for CO2 photoreduction into hydrocarbon fuels (CO and CH4). The process uses artificial sunlight as the energy source, water as an electron donor and CO2 as the carbon source, mimicking what real leaves do. To our knowledge this is the first example utilizing biological systems as “architecture-directing agents” for APS towards CO2 photoreduction, which hints at a more general principle for APS architectures with a great variety of optimized biological geometries. This research would have great significance for the potential realization of global carbon neutral cycle. PMID:23588925

Prediction of Change in Prescription Ingredient Costs and Co-payment Rates under a Reference Pricing System in South Korea.

PubMed

Heo, Ji Haeng; Rascati, Karen L; Lee, Eui-Kyung

2017-05-01

The reference pricing system (RPS) establishes reference prices within interchangeable reference groupings. For drugs priced higher than the reference point, patients pay the difference between the reference price and the total price. To predict potential changes in prescription ingredient costs and co-payment rates after implementation of an RPS in South Korea. Korean National Health Insurance claims data were used as a baseline to develop possible RPS models. Five components of a potential RPS policy were varied: reference groupings, reference pricing methods, co-pay reduction programs, manufacturer price reductions, and increased drug substitutions. The potential changes for prescription ingredient costs and co-payment rates were predicted for the various scenarios. It was predicted that transferring the difference (total price minus reference price) from the insurer to patients would reduce ingredient costs from 1.4% to 22.8% for the third-party payer (government), but patient co-payment rates would increase from a baseline of 20.4% to 22.0% using chemical groupings and to 25.0% using therapeutic groupings. Savings rates in prescription ingredient costs (government and patient combined) were predicted to range from 1.6% to 13.7% depending on various scenarios. Although the co-payment rate would increase, a 15% price reduction by manufacturers coupled with a substitution rate of 30% would result in a decrease in the co-payment amount (change in absolute dollars vs. change in rates). Our models predicted that the implementation of RPS in South Korea would lead to savings in ingredient costs for the third-party payer and co-payments for patients with potential scenarios. Copyright © 2017 International Society for Pharmacoeconomics and Outcomes Research (ISPOR). Published by Elsevier Inc. All rights reserved.

Organic synthesis during fluid mixing in hydrothermal systems

NASA Astrophysics Data System (ADS)

Shock, Everett L.; Schulte, Mitchell D.

1998-12-01

Hydrothermal circulation can lead to fluid mixing on any planet with liquid water and a source of heat. Aqueous fluids with differing compositions, especially different oxidation states, are likely to be far from thermodynamic equilibrium when they mix, and provide a source of free energy that can drive organic synthesis from CO2 and H2, and/or supply a source of geochemical energy to chemolithoautotrophic organisms. Results are presented that quantify the potential for organic synthesis during unbuffered fluid mixing in present submarine hydrothermal systems, as well as hypothetical systems that may have existed on the early Earth and Mars. Dissolved hydrogen, present in submarine hydrothermal fluids owing to the high-temperature reduction of H2O as seawater reacts with oceanic crustal rocks, provides the reduction potential and the thermodynamic drive for organic synthesis from CO2 (or bicarbonate) as hydrothermal fluids mix with seawater. The potential for organic synthesis is a strong function of the H2 content of the hydrothermal fluid, which is, in turn, a function of the prevailing oxidation state controlled by the composition of the rock that hosts the hydrothermal system. Hydrothermal fluids with initial oxidation states at or below those set by the fayalite-magnetite-quartz mineral assemblage show the greatest potential for driving organic synthesis. These calculations show that it is thermodynamically possible for 100% of the carbon in the mixed fluid to be reduced to a mixture of carboxylic acids, alcohols, and ketones in the range 250-50°C as cold seawater mixes with the hydrothermal fluid. As the temperature drops, larger organic molecules are favored, which implies that fluid mixing could drive the geochemical equivalent of a metabolic system. This enormous reduction potential probably drives a large portion of the primary productivity around present seafloor hydrothermal vents and would have been present in hydrothermal systems on the early Earth or Mars. The single largest control on the potential for organic synthesis is the composition of the rock that hosts the hydrothermal system.

Mass transport modelling for the electroreduction of CO2 on Cu nanowires

NASA Astrophysics Data System (ADS)

Raciti, David; Mao, Mark; Wang, Chao

2018-01-01

Mass transport plays an important role in CO2 reduction electrocatalysis. Albeit being more pronounced on nanostructured electrodes, the studies of mass transport for CO2 reduction have yet been limited to planar electrodes. We report here the development of a mass transport model for the electroreduction of CO2 on Cu nanowire electrodes. Fed with the experimental data from electrocatalytic studies, the local concentrations of CO2, {{{{HCO}}}3}-,{{{{CO}}}3}2- and OH- on the nanostructured electrodes are calculated by solving the diffusion equations with spatially distributed electrochemical reaction terms incorporated. The mass transport effects on the catalytic activity and selectivity of the Cu nanowire electrocatalysts are thus discussed by using the local pH as the descriptor. The established correlations between the electrocatalytic performance and the local pH shows that, the latter does not only determine the acid-base reaction equilibrium, but also regulates the mass transport and reaction kinetics. Based on these findings, the optimal range of local pH for CO2 reduction is discussed in terms of a fine balance among the suppression of hydrogen evolution, improvement of C2 product selectivity and limitation of CO2 supply. Our work highlights the importance of understanding the mass transport effects in interpretation of CO2 reduction electrocatalysis on high-surface-area catalysts.

Does Aerosol Geoengineering the Earth's Climate Pass a Cost-Benefit Test?

NASA Astrophysics Data System (ADS)

Keller, K.; Urban, N.; Tuana, N.

2007-12-01

Anthropogenic carbon dioxide (CO2) emissions are changing the Earth's climate with potentially dangerous consequences. Ratified international agreements call for a reduction of CO2 emissions to avoid dangerous anthropogenic interference with the climate system. Recent studies have, however, proposed an alternative strategy: to geoengineer Earth's climate by injecting aerosol precursors into the stratosphere. It is often claimed that aerosol geoengineering would provide net economic benefits because geoengineering requires far lower near-term investments compared to deep cuts in CO2 emissions. However, aerosol geoengineering projects can also cause nontrivial economic costs. This is because aerosol geoengineering hinges on successfully counterbalancing the forcing effects of CO2 emissions (which decay over centuries) with the forcing effects of aerosol emissions (which decay within years). A failure to maintain this delicate balance can lead to abrupt climatic changes, with potentially substantial economic damages. Deferring cuts in CO2 emissions in favor of aerosol geoengineering is hence a deeply uncertain gamble, as it requires so far unknown institutions to reliably control aerosol forcings over centuries. Here we use a simple economic model to evaluate potential costs and benefits of aerosol geoengineering for a wide range of the deeply uncertain parameters. We show that aerosol geoengineering projects may cause economic damages that can far exceed the benefits and may hence fail a cost-benefit test.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

PubMed

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

2017-06-27

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

PubMed Central

Favaro, Marco; Yano, Junko; Crumlin, Ethan J.

2017-01-01

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. PMID:28607092

Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*♦

PubMed Central

Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

2011-01-01

The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein α-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:21454640

The Carbon Dioxide Removal Model Intercomparison Project (CDRMIP): rationale and experimental protocol for CMIP6

NASA Astrophysics Data System (ADS)

Keller, David P.; Lenton, Andrew; Scott, Vivian; Vaughan, Naomi E.; Bauer, Nico; Ji, Duoying; Jones, Chris D.; Kravitz, Ben; Muri, Helene; Zickfeld, Kirsten

2018-03-01

The recent IPCC reports state that continued anthropogenic greenhouse gas emissions are changing the climate, threatening severe, pervasive and irreversible impacts. Slow progress in emissions reduction to mitigate climate change is resulting in increased attention to what is called geoengineering, climate engineering, or climate intervention - deliberate interventions to counter climate change that seek to either modify the Earth's radiation budget or remove greenhouse gases such as CO2 from the atmosphere. When focused on CO2, the latter of these categories is called carbon dioxide removal (CDR). Future emission scenarios that stay well below 2 °C, and all emission scenarios that do not exceed 1.5 °C warming by the year 2100, require some form of CDR. At present, there is little consensus on the climate impacts and atmospheric CO2 reduction efficacy of the different types of proposed CDR. To address this need, the Carbon Dioxide Removal Model Intercomparison Project (or CDRMIP) was initiated. This project brings together models of the Earth system in a common framework to explore the potential, impacts, and challenges of CDR. Here, we describe the first set of CDRMIP experiments, which are formally part of the 6th Coupled Model Intercomparison Project (CMIP6). These experiments are designed to address questions concerning CDR-induced climate reversibility, the response of the Earth system to direct atmospheric CO2 removal (direct air capture and storage), and the CDR potential and impacts of afforestation and reforestation, as well as ocean alkalinization.>

The Carbon Dioxide Removal Model Intercomparison Project (CDRMIP): rationale and experimental protocol for CMIP6

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

Keller, David P.; Lenton, Andrew; Scott, Vivian

The recent IPCC reports state that continued anthropogenic greenhouse gas emissions are changing the climate, threatening severe, pervasive and irreversible impacts. Slow progress in emissions reduction to mitigate climate change is resulting in increased attention to what is called geoengineering, climate engineering, or climate intervention – deliberate interventions to counter climate change that seek to either modify the Earth's radiation budget or remove greenhouse gases such as CO 2 from the atmosphere. When focused on CO 2, the latter of these categories is called carbon dioxide removal (CDR). Future emission scenarios that stay well below 2 °C, and all emissionmore » scenarios that do not exceed 1.5 °C warming by the year 2100, require some form of CDR. At present, there is little consensus on the climate impacts and atmospheric CO 2 reduction efficacy of the different types of proposed CDR. To address this need, the Carbon Dioxide Removal Model Intercomparison Project (or CDRMIP) was initiated. This project brings together models of the Earth system in a common framework to explore the potential, impacts, and challenges of CDR. Here, we describe the first set of CDRMIP experiments, which are formally part of the 6th Coupled Model Intercomparison Project (CMIP6). These experiments are designed to address questions concerning CDR-induced climate reversibility, the response of the Earth system to direct atmospheric CO 2 removal (direct air capture and storage), and the CDR potential and impacts of afforestation and reforestation, as well as ocean alkalinization.>« less

Use of glucose as reductant to recover Co from spent lithium ions batteries.

PubMed

Meng, Qi; Zhang, Yingjie; Dong, Peng

2017-06-01

A hydrometallurgical leaching process has been developed for recovery of Co and Li from cathode material (LiCoO 2 ) collected from spent LIBs using a mix solution of glucose and phosphoric acid. The spent LiCoO 2 before and after leaching process are analyzed by scanning electron microscopy. A leaching rate of about 98% Co and nearly 100% Li is presented with 1.5mol/L phosphoric acid and 0.02mol/L glucose at 80°C in about 2h. During leaching process, glucose was oxidized into monocarboxylic acid with reduction of Co(III) to Co(II). Co in solution was recovered as Co-oxalate after leaching process. Using glucose as reductant to dissolve LiCoO 2 with chelating agent of phosphoric acid is achieved here. Copyright © 2017 Elsevier Ltd. All rights reserved.

Global emissions of fluorinated greenhouse gases until 2050: technical mitigation potentials and costs

NASA Astrophysics Data System (ADS)

Purohit, Pallav; Hoglund-Isaksson, Lena

2016-04-01

The anthropogenic fluorinated (F-gases) greenhouse gas emissions have increased significantly in recent years and are estimated to rise further in response to increased demand for cooling services and the phase out of ozone-depleting substances (ODS) under the Montreal Protocol. F-gases (HFCs, PFCs and SF6) are potent greenhouse gases, with a global warming effect up to 22,800 times greater than carbon dioxide (CO2). This study presents estimates of current and future global emissions of F-gases, their technical mitigation potential and associated costs for the period 2005 to 2050. The analysis uses the GAINS model framework to estimate emissions, mitigation potentials and costs for all major sources of anthropogenic F-gases for 162 countries/regions, which are aggregated to produce global estimates. For each region, 18 emission source sectors with mitigation potentials and costs were identified. Global F-gas emissions are estimated at 0.7 Gt CO2eq in 2005 with an expected increase to about 3.6 Gt CO2eq in 2050. There are extensive opportunities to reduce emissions by over 95 percent primarily through replacement with existing low GWP substances. The initial results indicate that at least half of the mitigation potential is attainable at a cost of less than 20€ per t CO2eq, while almost 90 percent reduction is attainable at less than 100€ per t CO2eq. Currently, several policy proposals have been presented to amend the Montreal Protocol to substantially curb global HFC use. We analyze the technical potentials and costs associated with the HFC mitigation required under the different proposed Montreal Protocol amendments.

Production of Biomass-Based Automotive Lubricants by Reductive Etherification.

PubMed

Jadhav, Deepak; Grippo, Adam M; Shylesh, Sankaranarayanapillai; Gokhale, Amit A; Redshaw, John; Bell, Alexis T

2017-06-09

Growing concern with the effects of CO 2 emissions due to the combustion of petroleum-based transportation fuels has motivated the search for means to increase engine efficiency. The discovery of ethers with low viscosity presents an important opportunity to improve engine efficiency and fuel economy. We show here a strategy for the catalytic synthesis of such ethers by reductive etherification/O-alkylation of alcohols using building blocks that can be sourced from biomass. We find that long-chain branched ethers have several properties that make them superior lubricants to the mineral oil and synthetic base oils used today. These ethers provide a class of potentially renewable alternatives to conventional lubricants produced from petroleum and may contribute to the reduction of greenhouse gases associated with vehicle emissions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potential of solar domestic hot water systems in rural areas for greenhouse gas emission reduction in Poland

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

Skowronski, P.; Wisniewski, G.

Application of solar energy for preparing domestic hot water is one of the easiest methods of utilization of this energy. At least part of the needs for warm tap water could be covered by solar systems. At present, mainly coal is used for water heating at dwellings in rural areas in Poland. Warm tap water consumption will increase significantly in the future as standards of living are improved. This can result in the growth of electricity use and an increase in primary fuel consumption. Present and future methods of warm sanitary water generation in rural areas in Poland is discussed,more » and associated greenhouse gas (GHG) emissions are estimated. It is predicted that the emission of CO{sub 2} and NOx will increase. The emission of CO and CH{sub 4} will decrease because of changes in the structure of the final energy carriers used. The economic and market potentials of solar energy for preparing warm water in rural areas are discussed. It is estimated that solar systems can meet 30%-45% of the energy demand for warm water generation in rural areas at a reasonable cost, with a corresponding CO{sub 2} emission reduction. The rate of realization of the economic potential of solar water heaters depends on subsidies for the installation of equipment. 13 refs., 9 tabs.« less

Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

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

Jiang, Yi; Deng, Ya-Ping; Fu, Jing

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co 3O 4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co 3O 4@PGS) is synthesized via ionic exchange and redox between Co 2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells providesmore » an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co 3O 4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm -2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm -2 is achieved by Zn–air batteries with Co/Co 3O 4@PGS within the rechargeable air electrode.« less

Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

DOE PAGES

Jiang, Yi; Deng, Ya-Ping; Fu, Jing; ...

2018-01-31

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co 3O 4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co 3O 4@PGS) is synthesized via ionic exchange and redox between Co 2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells providesmore » an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co 3O 4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm -2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm -2 is achieved by Zn–air batteries with Co/Co 3O 4@PGS within the rechargeable air electrode.« less

A review on g-C3N4 for photocatalytic water splitting and CO2 reduction

NASA Astrophysics Data System (ADS)

Ye, Sheng; Wang, Rong; Wu, Ming-Zai; Yuan, Yu-Peng

2015-12-01

Solar fuel generation through water splitting and CO2 photoreduction is an ideal route to provide the renewable energy sources and mitigate global warming. The main challenge in photocatalysis is finding a low-cost photocatalyst that can work efficiently to split water into hydrogen and reduce CO2 to hydrocarbon fuels. Metal-free g-C3N4 photocatalyst shows great potentials for solar fuel production. In this mini review, we summarize the most current advances on novel design idea and new synthesis strategy for g-C3N4 preparation, insightful ideas on extending optical absorption of pristine g-C3N4, overall water splitting and CO2 photoreduction over g-C3N4 based systems. The research challenges and perspectives on g-C3N4 based photocatalysts were also suggested.

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

Rational Design of a Hierarchical Tin Dendrite Electrode for Efficient Electrochemical Reduction of CO2.

PubMed

Won, Da Hye; Choi, Chang Hyuck; Chung, Jaehoon; Chung, Min Wook; Kim, Eun-Hee; Woo, Seong Ihl

2015-09-21

Catalysis is a key technology for the synthesis of renewable fuels through electrochemical reduction of CO2 . However, successful CO2 reduction still suffers from the lack of affordable catalyst design and understanding the factors governing catalysis. Herein, we demonstrate that the CO2 conversion selectivity on Sn (or SnOx /Sn) electrodes is correlated to the native oxygen content at the subsurface. Electrochemical analyses show that the reduced Sn electrode with abundant oxygen species effectively stabilizes a CO2 (.-) intermediate rather than the clean Sn surface, and consequently results in enhanced formate production in the CO2 reduction. Based on this design strategy, a hierarchical Sn dendrite electrode with high oxygen content, consisting of a multi-branched conifer-like structure with an enlarged surface area, was synthesized. The electrode exhibits a superior formate production rate (228.6 μmol h(-1)  cm(-2) ) at -1.36 VRHE without any considerable catalytic degradation over 18 h of operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Southern Ocean biogeochemical control of glacial/interglacial carbon dioxide change

NASA Astrophysics Data System (ADS)

Sigman, D. M.

2014-12-01

In the effort to explain the lower atmospheric CO2 concentrations observed during ice ages, two of the first hypotheses involved redistributing dissolved inorganic carbon (DIC) within the ocean. Broecker (1982) proposed a strengthening of the ocean's biological pump during ice ages, which increased the dissolved inorganic carbon gradient between the dark, voluminous ocean interior and the surface ocean's sun-lit, wind-mixed layer. Boyle (1988) proposed a deepening in the ocean interior's pool of DIC associated with organic carbon regeneration, with its concentration maximum shifting from intermediate to abyssal depths. While not irrefutable, evidence has arisen that these mechanisms can explain much of the ice age CO2 reduction and that both were activated by changes in the Southern Ocean. In the Antarctic Zone, reduced exchange of water between the surface and the underlying ocean sequestered more DIC in the ocean interior (the biological pump mechanism). Dust-borne iron fertilization of the Subantarctic surface lowered CO2 partly by the biological pump mechanism and partly by Boyle's carbon deepening. Each mechanism owes a part of its CO2 effect to a transient increase in seafloor calcium carbonate dissolution, which raised the ice age ocean's alkalinity, causing it to absorb more CO2. However, calcium carbonate cycling also sets limits on these mechanisms and their CO2 effects, such that the combination of Antarctic and Subantarctic changes is needed to achieve the full (80-100 ppm) ice age CO2 decline. Data suggest that these changes began at different phases in the development of the last ice age, 110 and 70 ka, respectively, explaining a 40 ppm CO2 drop at each time. We lack a robust understanding of the potential causes for both the implied reduction in Antarctic surface/deep exchange and the increase in Subantarctic dust supply during ice ages. Thus, even if the evidence for these Southern Ocean changes were to become incontrovertible, conceptual gaps stand in the way of a theory of glacial cycles that includes Southern Ocean-driven CO2 change. There are more compelling proposals for the causes of deglacial change, with a sharp reduction in North Atlantic deep water formation implicated as a trigger of increased surface/deep exchange in the Antarctic and the resulting release of CO2 to the atmosphere.

Hydrogenation Reactions of CO and CO2: New Insights through In Situ X-ray Spectroscopy and Chemical Transient Kinetics Experiments on Cobalt Catalysts

NASA Astrophysics Data System (ADS)

Ralston, Walter Thomas

The catalytic hydrogenations of CO and CO2 to more useful chemicals is not only beneficial in producing more valuable products and reducing dependence on fossil fuels, but present a scientific challenge in how to control the selectivity of these reactions. Using colloidal chemistry techniques, a high level of control over the synthesis of nanomaterials can be achieved, and by exploiting this fact a simple model system can be realized to understand the reaction of CO and CO2 on a molecular level. Specifically, this dissertation focuses on understanding cobalt materials for the conversion of CO and CO2 into more useful, valuable chemicals. Colloidally prepared cobalt nanoparticles with a narrow size distribution were supported in mesoporous SiO2 and TiO2 to study the effect of the support on the Co catalyzed hydrogenation of CO and CO2. The 10nm Co/SiO2 and Co/TiO2 catalysts were tested for CO and CO2 hydrogenation at 5 bar with a ratio to hydrogen of 1:2 and 1:3, respectively. In addition, the effect of Co oxidation state was studied by using different reduction pretreatment temperatures (250°C and 450°C). The results showed that for both hydrogenation reactions, Co/TiO2 had a high activity at both reduction temperatures compared to Co/SiO2. However, unlike Co/SiO2 which showed higher activity after 450°C reduction, Co/TiO2 had a higher activity after reduction at 250°C. Through synchrotron x-ray spectroscopy, it was concluded that the TiO2 was wetting the Co particle at higher reduction temperatures and dewetting at lower reduction temperatures. In addition to the wetting, CoO was observed to be the surface species on Co/TiO2 catalyst after reduction at low temperatures, which catalyzed both CO and CO2 hydrogenation reactions with higher activity than the Co metal obtained after reduction at 450°C. Classical steady-state measurements are limited in so much as they are often unable to provide information on individual reaction steps in complex reaction pathways. To attempt to circumvent this, a chemical transient kinetics (CTK) reactor was designed and built. Verification of the reactor was performed by evaluating a catalyst from the literature and confirming the results. A CoMgO catalyst was used to accomplish this, and our original findings show that at short time scales steric hindrances at the surface may push the product distribution towards olefinic rather than branched compounds. Continuing work on the CTK, two distinct particle sizes of Co nanoparticles were synthesized and tested under atmospheric conditions (H2:CO = 2:1) on the transient reactor. 4.3 nm Co and 9.5 nm Co were supported on MCF-17 to study the previously observed size effect, where Co nanoparticles lose activity at smaller sizes. It was found that indeed, the 4.3 nm Co are less active because they contain less CO dissociation sites, which are necessary for populating the surface with carbon monomers and spurring subsequent chain growth. The specific CO dissociation site was identified as the Co (221) step, of which larger Co particles have more and smaller Co particles have less. To investigate the nature of the MnO / Co3O4 interface, an in situ study using synchrotron radiation was undertaken. A sample of 6nm MnO nanoparticles loaded on mesoporous Co3O4 was studied with ambient pressure x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy at the Mn and Co L edges, and scanning transmission x-ray microscopy. X-ray measurements show that under reducing conditions of CO + H2, the MnO nanoparticles wet the Co surface until it is completely covered by a layer of MnO. Through the combination of techniques, it is shown that the system is catalytic active at the low pressures studied, and that the nature of the interface between MnO and Co3O4 is highly dependent on the temperature and gaseous environment it is prepared in. (Abstract shortened by ProQuest.).

Interactions between bacterial carbon monoxide and hydrogen consumption and plant development on recent volcanic deposits.

PubMed

King, Gary M; Weber, Carolyn F

2008-02-01

Patterns of microbial colonization and interactions between microbial processes and vascular plants on volcanic deposits have received little attention. Previous reports have shown that atmospheric CO and hydrogen contribute significantly to microbial metabolism on Kilauea volcano (Hawaii) deposits with varied ages and successional development. Relationships between CO oxidation and plant communities were not clear, however, since deposit age and vegetation status covaried. To determine plant-microbe interactions in deposits of uniform ages, CO and hydrogen dynamics have been assayed for unvegetated tephra on a 1959 deposit at Pu'u Puai (PP-bare), at the edge of tree 'islands' within the PP deposit (PP-edge) and within PP tree islands (PP-canopy). Similar assays have been conducted for vegetated and unvegetated sites on a 1969 Mauna Ulu (MU) lava flow. Net in situ atmospheric CO uptake was highest at PP-edge and PP-bare sites (2.2+/-0.5 and 1.3+/-0.1 mg CO m(-2) day(-1), respectively), and least for PP-canopy (-3.2+/-0.9 mg CO m(-2) day(-1), net emission). Respiration rates, microbial biomass and maximum CO uptake potential showed an opposing pattern. Comparisons of atmospheric CO uptake and CO(2) production rates indicate that CO contributes significantly to microbial metabolism in PP-bare and MU-unvegetated sites, but negligibly where vegetation is well developed. Nonetheless, maximum potential CO uptake rates indicate that CO oxidizer populations increase with increasing plant biomass and consume CO actively. Some of these CO oxidizers may contribute to elevated nitrogen fixation rates (acetylene reduction) measured within tree islands, and thus, support plant successional development.

Plant Survival and Mortality during Drought Can be Mediated by Co-occurring Species' Physiological and Morphological Traits: Results from a Model

NASA Astrophysics Data System (ADS)

Tai, X.; Mackay, D. S.

2015-12-01

Interactions among co-occurring species are mediated by plant physiology, morphology and environment. Without proper mechanisms to account for these factors, it remains difficult to predict plant mortality/survival under changing climate. A plant ecophysiological model, TREES, was extended to incorporate co-occurring species' belowground interaction for water. We used it to examine the interaction between two commonly co-occurring species during drought experiment, pine (Pinus edulis) and juniper (Juniperus monosperma), with contrasting physiological traits (vulnerability to cavitation and leaf water potential regulation). TREES was parameterized and validated using field-measured plant physiological traits. The root architecture (depth, profile, and root area to leaf area ratio) of juniper was adjusted to see how root morphology could affect the survival/mortality of its neighboring pine under both ambient and drought conditions. Drought suppressed plant water and carbon uptake, as well increased the average percentage loss of conductivity (PLC). Pine had 59% reduction in water uptake, 48% reduction in carbon uptake, and 38% increase in PLC, while juniper had 56% reduction in water uptake, 50% reduction in carbon and 29% increase in PLC, suggesting different vulnerability to drought as mediated by plant physiological traits. Variations in juniper root architecture further mediated drought stress on pine, from negative to positive. Different juniper root architecture caused variations in response of pine over drought (water uptake reduction ranged 0% ~63%, carbon uptake reduction ranged 0% ~ 70%, and PLC increase ranged 2% ~ 91%). Deeper or more uniformly distributed roots of juniper could effectively mitigate stress experienced by pine. In addition, the total water and carbon uptake tended to increase as the ratio of root area to leaf area increased while PLC showed non-monotonic response, suggesting the potential trade-off between maximizing resource uptake and susceptibility to cavitation. The results showed that co-occurring species' morphological traits could alleviate or aggravate stress imposed by drought and should therefore be considered together with plant physiological traits in predicting plant mortality and ecosystem structural shift under future climate conditions.

Climate, Air Quality, and Human Health Benefits of Various Solar Photovoltaic Development Scenarios in China in 2030

NASA Astrophysics Data System (ADS)

Yang, J.; Mauzerall, D. L.; Wagner, F.; Li, X.

2016-12-01

Solar photovoltaic (PV) technology can greatly reduce both air pollution and GHG emissions from the power sector. The Chinese government has plans to scale up solar PV installation between now and 2030. However, there is little analysis of how deployment strategies will influence the range of benefits. Here we conduct the first integrated assessment study that quantifies the climate, air quality, and related human health benefits of various solar PV development strategies in 2030 China. Our results indicate that both the location of PV deployment, which coal power plants are replaced, and the extent of inter-provincial transmission greatly influence the co-benefits. We compare CO2 and PM2.5 reductions from two PV installation scenarios both with the 2030 government target of 400 GW national installed capacity. First, we assume all solar PV is utilized within the province in which it is generated and that it can not exceed 30% of total provincial electricity generation. We find that deploying more solar PV in locations near load centers via distributed PV systems has larger benefits and could lead to approximately 20,500 (between 8000 - 32,400, high and low bounds) annual avoided premature deaths, 15% more than building utility-scale solar PV plants in the sunny, yet sparsely populated northwest. The difference occurs because in the northwest a lower population and cleaner air leads to smaller reductions in air pollution related premature mortalities. Also greater potential for PV curtailment exists in the west. In terms of CO2 reduction, deploying PV near load centers leads to 12% greater reductions in CO2 emissions from the power sector - approximately 5% of China's total CO2 emission in 2030. Second, we enable inter-provincial transmission of PV electricity within each of China's six regional grids which allows greater use of abundant sunlight in the northwest. Our results for 2030 show that by expanding to the regional grid, curtailment rates in the northwest would drop from 25% to 14%, and additional reductions of 30% SO2 and 25% NOxfrom the power sector would result. Thus our study demonstrates substantial air quality and climate co-benefits of developing solar PV in China. We also find that expanding inter-provincial electricity transmission would both reduce curtailment and increase air quality benefits.

Solvent-driven reductive activation of carbon dioxide by gold anions.

PubMed

Knurr, Benjamin J; Weber, J Mathias

2012-11-14

Catalytic activation and electrochemical reduction of CO(2) for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle. The role of solvent molecules in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass-selected Au(CO(2))(n)(-) cluster ions to probe the solvation of AuCO(2)(-) as a model for a reactive intermediate in the reductive activation of a CO(2) ligand by a single-atom catalyst. For the first few solvent molecules, solvation of the complex preferentially occurs at the CO(2) moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional solvent molecules with the Au atom diminishes reduction. The results show how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single-atom catalyst engineering.

Electrochemical quartz crystal microbalance analysis of the oxygen reduction reaction on Pt-based electrodes. Part 2: adsorption of oxygen species and ClO4(-) anions on Pt and Pt-Co alloy in HClO4 solutions.

PubMed

Omura, J; Yano, H; Tryk, D A; Watanabe, M; Uchida, H

2014-01-14

To gain deeper insight into the role of adsorbed oxygenated species in the O2 reduction reaction (ORR) kinetics on platinum and platinum-cobalt alloys for fuel cells, we carried out a series of measurements with the electrochemical quartz crystal microbalance (EQCM) and the rotating disk electrode (RDE) in acid solution. The effects of anion adsorption on the activities for the ORR were first assessed in HClO4 and HF electrolyte solutions at various concentrations. In our previous work (Part 1), we reported that the perchlorate anion adsorbs specifically on bulk-Pt, with a Frumkin-Temkin isotherm, that is, a linear relationship between Δm and log[HClO4]. Here, we find that the specific adsorption on the Pt-skin/Pt3Co alloy was significantly stronger than that on bulk-Pt, in line with its modified electronic properties. The kinetically controlled current density j(k) for the O2 reduction at the Pt-skin/Pt3Co-RDE was about 9 times larger than that of the bulk-Pt-RDE in 0.01 M HClO4 saturated with air, but the j(k) values on Pt-skin/Pt3Co decreased with increasing [HClO4] more steeply than in the case of Pt, due to the blocking of the active sites by the specifically adsorbed ClO4(-). We have detected reversible mass changes for one or more adsorbed oxygen-containing species (Ox = O2, O, OH, H2O) on the Pt-skin/Pt3Co-EQCM and Pt-EQCM in O2-saturated and He-purged 0.01 M HClO4 solutions, in which the specific adsorption of ClO4(-) anions was negligible. The coverages of oxygen species θ(Ox) on the Pt-skin/Pt3Co in the potential range from 0.86 to 0.96 V in the O2-saturated solution were found to be larger than those on pure Pt, providing strong evidence that the higher O2 reduction activity on the Pt3Co is correlated with higher θ(Ox), contrary to the conventional view.

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

Rational Design of Bi Nanoparticles for Efficient Electrochemical CO 2 Reduction: The Elucidation of Size and Surface Condition Effects

DOE PAGES

Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

2016-08-08

Here we report an efficient electrochemical conversion of CO 2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO 2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi 3+ species) formed during the synthesis and purification process hinders the CO 2 reduction, leading to a 20% drop in Faradaic efficiency formore » CO evolution (FE CO). Bi particle size showed a significant effect on FE CO when the surface of Bi was air-oxidized, but this effect of size on FE CO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO 2 to CO (96.1% FE CO), and a mass activity for CO evolution (MA CO) of 15.6 mA mg –1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO 2 conversion on metal NPs and paves the way for understanding the CO 2 electrochemical reduction mechanism in nonaqueous media.« less

Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

2015-12-01

Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

CO2 to methanol conversion using hydride terminated porous silicon nanoparticles.

PubMed

Dasog, M; Kraus, S; Sinelnikov, R; Veinot, J G C; Rieger, B

2017-03-09

Porous silicon nanoparticles (Si-NPs) prepared via magnesiothermic reduction were used to convert carbon dioxide (CO 2 ) into methanol. The hydride surface of the silicon nanoparticles acted as a CO 2 reducing reagent without any catalyst at temperatures above 100 °C. The Si nanoparticles were reused up to four times without significant loss in methanol yields. The reduction process was monitored using in situ FT-IR and the materials were characterized using SEM, TEM, NMR, XPS, and powder XRD techniques. The influence of reaction temperature, pressure, and Si-NP concentration on CO 2 reduction were also investigated. Finally, Si particles produced directly from sand were used to convert CO 2 to methanol.

In-situ Production of High Density Polyethylene and Other Useful Materials on Mars

NASA Technical Reports Server (NTRS)

Flynn, Michael

2005-01-01

This paper describes a revolutionary materials structure and power storage concept based on the in-situ production of abiotic carbon 4 compounds. One of the largest single mass penalties required to support the human exploration of Mars is the surface habitat. This proposal will use physical chemical technologies to produce high density polyethylene (HDPE) inflatable structures and construction materials from Mars atmospheric CO2. The formation of polyethylene from Mars CO2 is based on the use of the Sabatier and modified Fischer Tropsch reactions. The proposed system will fully integrate with existing in-situ propellant production concepts. The technology will also be capable of supplementing human caloric requirements, providing solid and liquid fuels for energy storage, and providing significant reduction in mission risk. The NASA Mars Reference Mission Definition Team estimated that a conventional Mars surface habitat structure would weigh 10 tonnes. It is estimated that this technology could reduce this mass by 80%. This reduction in mass will significantly contribute to the reduction in total mission cost need to make a Mars mission a reality. In addition the potential reduction of risk provided by the ability to produce C4 and potentially higher carbon based materials in-situ on Mars is significant. Food, fuel, and shelter are only three of many requirements that would be impacted by this research.

Coupled Ferredoxin and Crotonyl Coenzyme A (CoA) Reduction with NADH Catalyzed by the Butyryl-CoA Dehydrogenase/Etf Complex from Clostridium kluyveri▿ †

PubMed Central

Li, Fuli; Hinderberger, Julia; Seedorf, Henning; Zhang, Jin; Buckel, Wolfgang; Thauer, Rudolf K.

2008-01-01

Cell extracts of butyrate-forming clostridia have been shown to catalyze acetyl-coenzyme A (acetyl-CoA)- and ferredoxin-dependent formation of H2 from NADH. It has been proposed that these bacteria contain an NADH:ferredoxin oxidoreductase which is allosterically regulated by acetyl-CoA. We report here that ferredoxin reduction with NADH in cell extracts from Clostridium kluyveri is catalyzed by the butyryl-CoA dehydrogenase/Etf complex and that the acetyl-CoA dependence previously observed is due to the fact that the cell extracts catalyze the reduction of acetyl-CoA with NADH via crotonyl-CoA to butyryl-CoA. The cytoplasmic butyryl-CoA dehydrogenase complex was purified and is shown to couple the endergonic reduction of ferredoxin (E0′ = −410 mV) with NADH (E0′ = −320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (E0′ = −10 mV) with NADH. The stoichiometry of the fully coupled reaction is extrapolated to be as follows: 2 NADH + 1 oxidized ferredoxin + 1 crotonyl-CoA = 2 NAD+ + 1 ferredoxin reduced by two electrons + 1 butyryl-CoA. The implications of this finding for the energy metabolism of butyrate-forming anaerobes are discussed in the accompanying paper. PMID:17993531

Uranium-mediated electrocatalytic dihydrogen production from water.

PubMed

Halter, Dominik P; Heinemann, Frank W; Bachmann, Julien; Meyer, Karsten

2016-02-18

Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1 - 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [(((Ad,Me)ArO)3mes)U] (refs 18 and 19)--the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium--an abundant waste product of the nuclear power industry--could be a valuable resource.

The impacts of effective stress and CO 2 sorption on the matrix permeability of shale reservoir rocks [The impacts of CO 2 sorption and effective stress on the matrix permeability of shale reservoir rocks

DOE PAGES

Wu, Wei; Zoback, Mark D.; Kohli, Arjun H.

2017-05-02

We assess the impacts of effective stress and CO 2 sorption on the bedding-parallel matrix permeability of the Utica shale through pressure pulse-decay experiments. We first measure permeability using argon at relatively high (14.6 MPa) and low (2.8 MPa) effective stresses to assess both pressure dependence and recoverability. We subsequently measure permeability using supercritical CO 2 and again using argon to assess changes due to CO 2 sorption. We find that injection of both argon and supercritical CO 2 reduces matrix permeability in distinct fashion. Samples with permeability higher than 10 –20 m 2 experience a large permeability reduction aftermore » treatment with argon, but a minor change after treatment with supercritical CO 2. However, samples with permeability lower than this threshold undergo a slight change after treatment with argon, but a dramatic reduction after treatment with supercritical CO 2. These results indicate that effective stress plays an important role in the evolution of relatively permeable facies, while CO 2 sorption dominates the change of ultra-low permeability facies. The permeability reduction due to CO 2 sorption varies inversely with initial permeability, which suggests that increased surface area from hydraulic stimulation with CO 2 may be counteracted by sorption effects in ultra-low permeability facies. As a result, we develop a conceptual model to explain how CO 2 sorption induces porosity reduction and volumetric expansion to constrict fluid flow pathways in shale reservoir rocks.« less

The impacts of effective stress and CO 2 sorption on the matrix permeability of shale reservoir rocks [The impacts of CO 2 sorption and effective stress on the matrix permeability of shale reservoir rocks

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

Wu, Wei; Zoback, Mark D.; Kohli, Arjun H.

We assess the impacts of effective stress and CO 2 sorption on the bedding-parallel matrix permeability of the Utica shale through pressure pulse-decay experiments. We first measure permeability using argon at relatively high (14.6 MPa) and low (2.8 MPa) effective stresses to assess both pressure dependence and recoverability. We subsequently measure permeability using supercritical CO 2 and again using argon to assess changes due to CO 2 sorption. We find that injection of both argon and supercritical CO 2 reduces matrix permeability in distinct fashion. Samples with permeability higher than 10 –20 m 2 experience a large permeability reduction aftermore » treatment with argon, but a minor change after treatment with supercritical CO 2. However, samples with permeability lower than this threshold undergo a slight change after treatment with argon, but a dramatic reduction after treatment with supercritical CO 2. These results indicate that effective stress plays an important role in the evolution of relatively permeable facies, while CO 2 sorption dominates the change of ultra-low permeability facies. The permeability reduction due to CO 2 sorption varies inversely with initial permeability, which suggests that increased surface area from hydraulic stimulation with CO 2 may be counteracted by sorption effects in ultra-low permeability facies. As a result, we develop a conceptual model to explain how CO 2 sorption induces porosity reduction and volumetric expansion to constrict fluid flow pathways in shale reservoir rocks.« less

Investigation of industrial-scale carbon dioxide reduction using pulsed electron beams

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

Petrov, G. M.; Apruzese, J. P.; Petrova, Tz. B.

Carbon dioxide is the most important greenhouse gas contributing to global warming. To help mitigate increasing CO{sub 2} concentrations, we investigate a method of carbon dioxide reduction using high-power electron beams, which can be used on an industrial scale. A series of experiments are conducted in which the reduction of CO{sub 2} is measured for different gas compositions and power deposition rates. An electron beam deposition model is applied to compute reduction rates of CO{sub 2} and energy cost for breaking a CO{sub 2} molecule in flue gas and pure carbon dioxide at atmospheric pressure. For flue gas consisting ofmore » 82% N{sub 2}, 6% O{sub 2}, and 12% CO{sub 2}, the calculated energy cost is 85 eV per molecule. In order to dissociate 50% of the CO{sub 2} molecules, beam energy density deposition on the order of 20 J/cm{sup 3} is required. Electron beam irradiation of 12.6 liter gas volume containing 90% CO{sub 2} and 10% CH{sub 4} at beam energy density deposition of 4.2 J/cm{sup 3}, accumulated over 43 shots in a 20 min interval, reduced the CO{sub 2} concentration to 78%. Analogous experiments with a gas mixture containing 11.5% CO{sub 2}, 11.5% CH{sub 4}, and balance of Ar, reduced the CO{sub 2} concentration to below 11% with energy deposition 0.71 J/cm{sup 3}, accumulated over 10 shots in a 5 min interval. The experimental data and the theoretical predictions of CO{sub 2} reduction using pulsed electron beams are in agreement within the experimental error. Other techniques to enhance the removal of CO{sub 2} with pulsed electron beams are also explored, yielding new possible avenues of research.« less

Pressurized chemical-looping combustion of coal with an iron ore-based oxygen carrier

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

Xiao, Rui; Song, Min; Zhang, Shuai

2010-06-15

Chemical-looping combustion (CLC) is a new combustion technology with inherent separation of CO{sub 2}. Most of the previous investigations on CLC of solid fuels were conducted under atmospheric pressure. A pressurized CLC combined cycle (PCLC-CC) system is proposed as a promising coal combustion technology with potential higher system efficiency, higher fuel conversion, and lower cost for CO{sub 2} sequestration. In this study pressurized CLC of coal with Companhia Valedo Rio Doce (CVRD) iron ore was investigated in a laboratory fixed bed reactor. CVRD iron ore particles were exposed alternately to reduction by 0.4 g of Chinese Xuzhou bituminous coal gasifiedmore » with 87.2% steam/N{sub 2} mixture and oxidation with 5% O{sub 2} in N{sub 2} at 970 C. The operating pressure was varied between 0.1 MPa and 0.6 MPa. First, control experiments of steam coal gasification over quartz sand were performed. H{sub 2} and CO{sub 2} are the major components of the gasification products, and the operating pressure influences the gas composition. Higher concentrations of CO{sub 2} and lower fractions of CO, CH{sub 4}, and H{sub 2} during the reduction process with CVRD iron ore was achieved under higher pressures. The effects of pressure on the coal gasification rate in the presence of the oxygen carrier were different for pyrolysis and char gasification. The pressurized condition suppresses the initial coal pyrolysis process while it also enhances coal char gasification and reduction with iron ore in steam, and thus improves the overall reaction rate of CLC. The oxidation rates and variation of oxygen carrier conversion are higher at elevated pressures reflecting higher reduction level in the previous reduction period. Scanning electron microscope and energy-dispersive X-ray spectroscopy (SEM-EDX) analyses show that particles become porous after experiments but maintain structure and size after several cycles. Agglomeration was not observed in this study. An EDX analysis demonstrates that there is very little coal ash deposited on the oxygen carrier particles but no appreciable crystalline phases change as verified by X-ray diffraction (XRD) analysis. Overall, the limited pressurized CLC experiments carried out in the present work suggest that PCLC of coal is promising and further investigations are necessary. (author)« less

CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives.

PubMed

Han, Zhiji; Kortlever, Ruud; Chen, Hsiang-Yun; Peters, Jonas C; Agapie, Theodor

2017-08-23

Electrocatalytic CO 2 reduction to generate multicarbon products is of interest for applications in artificial photosynthetic schemes. This is a particularly attractive goal for CO 2 reduction by copper electrodes, where a broad range of hydrocarbon products can be generated but where selectivity for C-C coupled products relative to CH 4 and H 2 remains an impediment. Herein we report a simple yet highly selective catalytic system for CO 2 reduction to C ≥2 hydrocarbons on a polycrystalline Cu electrode in bicarbonate aqueous solution that uses N-substituted pyridinium additives. Selectivities of 70-80% for C 2 and C 3 products with a hydrocarbon ratio of C ≥2 /CH 4 significantly greater than 100 have been observed with several additives. 13 C-labeling studies verify CO 2 to be the sole carbon source in the C ≥2 hydrocarbons produced. Upon electroreduction, the N-substituted pyridinium additives lead to film deposition on the Cu electrode, identified in one case as the reductive coupling product of N -arylpyridinium. Product selectivity can also be tuned from C ≥2 species to H 2 (∼90%) while suppressing methane with certain N-heterocyclic additives.

Electrochemical CO2 Reduction via Gas-Phase Catholyte

NASA Astrophysics Data System (ADS)

Carter, Brittany E.; Nesbitt, Nathan T.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Vermaas, David A.; Smith, Wilson A.; Naughton, Michael J.

Reducing CO2 to CO through electrolysis, for the eventual conversion to hydrocarbons, provides a path towards utility-scale seasonal storage of renewable energy. Electrochemical reduction of CO2 has previously been achieved using a two chamber system. The chambers are typically separated by a semipermeable Nafion membrane, with an oxygen evolution catalyst anode on one side, a gold cathode on the other, and a solution containing CO2 on both sides. If instead, CO2 gas was in the second chamber, the reaction should yield more CO formed from CO2 at a given overpotential; this would result from the increased concentration of CO2 at the cathode surface and more facile mass transport of the CO and CO2. With liquid in one chamber and gas in the other, electrolysis is performed by integrating the cathode onto the semipermeable Nafion membrane. This membrane electrode assembly is fabricated via nanoimprint lithography (NIL), simultaneously achieving high active surface area and permeability. Challenges to the Nafion NIL process, and the performance of the system in CO2 reduction, will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant

NASA Technical Reports Server (NTRS)

Schoonen, M. A.; Xu, Y.; Bebie, J.

1999-01-01

The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature. This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature. By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature. Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature. An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable. By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile. This theoretical analysis explains the results of experimental work by Keefe et al. (1995), Heinen and Lauwers (1996) and Huber and Wachtershauser (1997). The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wachtershauser, 1988b; 1990b, 1990a, 1992, 1993).

Surface Immobilization of Transition Metal Ions on Nitrogen-Doped Graphene Realizing High-Efficient and Selective CO2 Reduction.

PubMed

Bi, Wentuan; Li, Xiaogang; You, Rui; Chen, Minglong; Yuan, Ruilin; Huang, Weixin; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2018-05-01

Electrochemical conversion of CO 2 to value-added chemicals using renewable electricity provides a promising way to mitigate both global warming and the energy crisis. Here, a facile ion-adsorption strategy is reported to construct highly active graphene-based catalysts for CO 2 reduction to CO. The isolated transition metal cyclam-like moieties formed upon ion adsorption are found to contribute to the observed improvements. Free from the conventional harsh pyrolysis and acid-leaching procedures, this solution-chemistry strategy is easy to scale up and of general applicability, thus paving a rational avenue for the design of high-efficiency catalysts for CO 2 reduction and beyond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Chemical approaches to carbon dioxide utilization for manned Mars missions

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Landis, Geoffrey A.; Kubiak, Clifford P.

1991-01-01

Use of resources available in situ is a critical enabling technology for a permanent human presence in space. A permanent presence on Mars, e.g., requires a large infrastructure to sustain life under hostile conditions. As a resource on Mars, atmospheric CO2 is as follows: abundant; available at all points on the surface; of known presence; chemically simple; and can be obtained by simple compression. Many studies focus on obtaining O2 and the various uses for O2 including life support and fuel; discussion of CO, the coproduct from CO2 fixation revolves around its uses as a fuel, being oxidized back to CO2. Several new proposals are studied for CO2 fixation through chemical, photochemical, and photoelectrochemical means. For example, the reduction of CO2 to hydrocarbons such as acetylene (C2H2) can be accomplished with H2. C2H2 has a theoretical vacuum specific impulse of approx. 375 secs. Potential uses were also studied of CO2, as obtained or further reduced to carbon, as a reducing agent in metal oxide processing to form metals or metal carbides for use as structural or power materials; the CO2 can be recycled to generate O2 and CO.

Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

PubMed

Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

2014-04-01

Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

An Aurivillius Oxide Based Cathode with Excellent CO2 Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

PubMed

Zhu, Yinlong; Zhou, Wei; Chen, Yubo; Shao, Zongping

2016-07-25

The Aurivillius oxide Bi2 Sr2 Nb2 MnO12-δ (BSNM) was used as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). To the best of our knowledge, the BSNM oxide is the only alkaline-earth-containing cathode material with complete CO2 tolerance that has been reported thus far. BSNM not only shows favorable activity in the oxygen reduction reaction (ORR) at intermediate temperatures but also exhibits a low thermal expansion coefficient, excellent structural stability, and good chemical compatibility with the electrolyte. These features highlight the potential of the new BSNM material as a highly promising cathode material for IT-SOFCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Climate change impacts of US reactive nitrogen.

PubMed

Pinder, Robert W; Davidson, Eric A; Goodale, Christine L; Greaver, Tara L; Herrick, Jeffrey D; Liu, Lingli

2012-05-15

Fossil fuel combustion and fertilizer application in the United States have substantially altered the nitrogen cycle, with serious effects on climate change. The climate effects can be short-lived, by impacting the chemistry of the atmosphere, or long-lived, by altering ecosystem greenhouse gas fluxes. Here we develop a coherent framework for assessing the climate change impacts of US reactive nitrogen emissions, including oxides of nitrogen, ammonia, and nitrous oxide (N(2)O). We use the global temperature potential (GTP), calculated at 20 and 100 y, in units of CO(2) equivalents (CO(2)e), as a common metric. The largest cooling effects are due to combustion sources of oxides of nitrogen altering tropospheric ozone and methane concentrations and enhancing carbon sequestration in forests. The combined cooling effects are estimated at -290 to -510 Tg CO(2)e on a GTP(20) basis. However, these effects are largely short-lived. On a GTP(100) basis, combustion contributes just -16 to -95 Tg CO(2)e. Agriculture contributes to warming on both the 20-y and 100-y timescales, primarily through N(2)O emissions from soils. Under current conditions, these warming and cooling effects partially offset each other. However, recent trends show decreasing emissions from combustion sources. To prevent warming from US reactive nitrogen, reductions in agricultural N(2)O emissions are needed. Substantial progress toward this goal is possible using current technology. Without such actions, even greater CO(2) emission reductions will be required to avoid dangerous climate change.

Climate change impacts of US reactive nitrogen

PubMed Central

Pinder, Robert W.; Davidson, Eric A.; Goodale, Christine L.; Greaver, Tara L.; Herrick, Jeffrey D.; Liu, Lingli

2012-01-01

Fossil fuel combustion and fertilizer application in the United States have substantially altered the nitrogen cycle, with serious effects on climate change. The climate effects can be short-lived, by impacting the chemistry of the atmosphere, or long-lived, by altering ecosystem greenhouse gas fluxes. Here we develop a coherent framework for assessing the climate change impacts of US reactive nitrogen emissions, including oxides of nitrogen, ammonia, and nitrous oxide (N2O). We use the global temperature potential (GTP), calculated at 20 and 100 y, in units of CO2 equivalents (CO2e), as a common metric. The largest cooling effects are due to combustion sources of oxides of nitrogen altering tropospheric ozone and methane concentrations and enhancing carbon sequestration in forests. The combined cooling effects are estimated at −290 to −510 Tg CO2e on a GTP20 basis. However, these effects are largely short-lived. On a GTP100 basis, combustion contributes just −16 to −95 Tg CO2e. Agriculture contributes to warming on both the 20-y and 100-y timescales, primarily through N2O emissions from soils. Under current conditions, these warming and cooling effects partially offset each other. However, recent trends show decreasing emissions from combustion sources. To prevent warming from US reactive nitrogen, reductions in agricultural N2O emissions are needed. Substantial progress toward this goal is possible using current technology. Without such actions, even greater CO2 emission reductions will be required to avoid dangerous climate change. PMID:22547815

On sorption and swelling of CO 2 in clays

DOE PAGES

Busch, A.; Bertier, P.; Gensterblum, Y.; ...

2016-03-23

One well-studied technology is the geological storage of carbon dioxide (CO 2), and a number of demonstration projects around the world have proven its feasibility and challenges. Storage conformance and seal integrity are among the most important aspects, as they determine risk of leakage as well as limits for storage capacity and injectivity. By providing evidence for safe storage is critical for improving public acceptance. Most caprocks are composed of clays as dominant mineral type which can typically be illite, kaolinite, chlorite or smectite. A number of recent studies addressed the interaction between CO 2 and these different clays andmore » it was shown that clay minerals adsorb considerable quantities of CO 2. For smectite this uptake can lead to volumetric expansion followed by the generation of swelling pressures. On the one hand CO 2 adsorption traps CO 2, on the other hand swelling pressures can potentially change local stress regimes and in unfavourable situations shear-type failure is assumed to occur. Moreover, for storage in a reservoir having high clay contents the CO 2 uptake can add to storage capacity which is widely underestimated so far. Smectite-rich seals in direct contact with a dry CO 2 plume at the interface to the reservoir might dehydrate leading to dehydration cracks. Such dehydration cracks can provide pathways for CO 2 ingress and further accelerate dewatering and penetration of the seal by supercritical CO 2. At the same time, swelling may also lead to the closure of fractures or the reduction of fracture apertures, thereby improving seal integrity. Finally, the goal of this communication is to theoretically evaluate and discuss these scenarios in greater detail in terms of phenomenological mechanisms, but also in terms of potential risks or benefits for carbon storage.« less

Photocatalytic reduction of CO2 by employing ZnO/Ag1-xCux/CdS and related heterostructures

NASA Astrophysics Data System (ADS)

Lingampalli, S. R.; Ayyub, Mohd Monis; Magesh, Ganesan; Rao, C. N. R.

2018-01-01

In view of the great importance of finding ways to reduce CO2 by using solar energy, we have examined the advantage of employing heterostructures containing bimetallic alloys for the purpose. This choice is based on the knowledge that metals such as Pt reduce CO2, although the activity may not be considerable. Our studies on the reduction of CO2 by ZnO/M/CdS (M = Ag, Au, Ag1-xAux, Ag1-xCux) heterostructures in liquid phase have shown good results specially in the case of ZnO/Ag1-xCux/CdS, reaching a CO production activity of 327.4 μmol h-1 g-1. The heterostructures also reduce CO2 in the gas-phase although the production activity is not high. Some of the heterostructures exhibit reduction of CO2 even in the absence of a sacrificial reagent.

Towards Verifying National CO2 Emissions

NASA Astrophysics Data System (ADS)

Fung, I. Y.; Wuerth, S. M.; Anderson, J. L.

2017-12-01

With the Paris Agreement, nations around the world have pledged their voluntary reductions in future CO2 emissions. Satellite observations of atmospheric CO2 have the potential to verify self-reported emission statistics around the globe. We present a carbon-weather data assimilation system, wherein raw weather observations together with satellite observations of the mixing ratio of column CO2 from the Orbiting Carbon Observatory-2 are assimilated every 6 hours into the NCAR carbon-climate model CAM5 coupled to the Ensemble Kalman Filter of DART. In an OSSE, we reduced the fossil fuel emissions from a country, and estimated the emissions innovations demanded by the atmospheric CO2 observations. The uncertainties in the innovation are analyzed with respect to the uncertainties in the meteorology to determine the significance of the result. The work follows from "On the use of incomplete historical data to infer the present state of the atmosphere" (Charney et al. 1969), which maps the path for continuous data assimilation for weather forecasting and the five decades of progress since.

Advanced CO2 Removal and Reduction System

NASA Technical Reports Server (NTRS)

Alptekin, Gokhan; Dubovik, Margarita; Copeland, Robert J.

2011-01-01

An advanced system for removing CO2 and H2O from cabin air, reducing the CO2, and returning the resulting O2 to the air is less massive than is a prior system that includes two assemblies . one for removal and one for reduction. Also, in this system, unlike in the prior system, there is no need to compress and temporarily store CO2. In this present system, removal and reduction take place within a single assembly, wherein removal is effected by use of an alkali sorbent and reduction is effected using a supply of H2 and Ru catalyst, by means of the Sabatier reaction, which is CO2 + 4H2 CH4 + O2. The assembly contains two fixed-bed reactors operating in alternation: At first, air is blown through the first bed, which absorbs CO2 and H2O. Once the first bed is saturated with CO2 and H2O, the flow of air is diverted through the second bed and the first bed is regenerated by supplying it with H2 for the Sabatier reaction. Initially, the H2 is heated to provide heat for the regeneration reaction, which is endothermic. In the later stages of regeneration, the Sabatier reaction, which is exothermic, supplies the heat for regeneration.

Reviews and Syntheses: Ocean acidification and its potential impacts on marine ecosystems

NASA Astrophysics Data System (ADS)

Mostofa, Khan M. G.; Liu, Cong-Qiang; Zhai, WeiDong; Minella, Marco; Vione, Davide; Gao, Kunshan; Minakata, Daisuke; Arakaki, Takemitsu; Yoshioka, Takahito; Hayakawa, Kazuhide; Konohira, Eiichi; Tanoue, Eiichiro; Akhand, Anirban; Chanda, Abhra; Wang, Baoli; Sakugawa, Hiroshi

2016-03-01

Ocean acidification, a complex phenomenon that lowers seawater pH, is the net outcome of several contributions. They include the dissolution of increasing atmospheric CO2 that adds up with dissolved inorganic carbon (dissolved CO2, H2CO3, HCO3-, and CO32-) generated upon mineralization of primary producers (PP) and dissolved organic matter (DOM). The aquatic processes leading to inorganic carbon are substantially affected by increased DOM and nutrients via terrestrial runoff, acidic rainfall, increased PP and algal blooms, nitrification, denitrification, sulfate reduction, global warming (GW), and by atmospheric CO2 itself through enhanced photosynthesis. They are consecutively associated with enhanced ocean acidification, hypoxia in acidified deeper seawater, pathogens, algal toxins, oxidative stress by reactive oxygen species, and thermal stress caused by longer stratification periods as an effect of GW. We discuss the mechanistic insights into the aforementioned processes and pH changes, with particular focus on processes taking place with different timescales (including the diurnal one) in surface and subsurface seawater. This review also discusses these collective influences to assess their potential detrimental effects to marine organisms, and of ecosystem processes and services. Our review of the effects operating in synergy with ocean acidification will provide a broad insight into the potential impact of acidification itself on biological processes. The foreseen danger to marine organisms by acidification is in fact expected to be amplified by several concurrent and interacting phenomena.