First identification and thermodynamic characterization of the ternary U(VI) species, UO2(O2)(CO3)2(4-), in UO2-H2O2-K2CO3 solutions.

PubMed

Goff, George S; Brodnax, Lia F; Cisneros, Michael R; Peper, Shane M; Field, Stephanie E; Scott, Brian L; Runde, Wolfgang H

2008-03-17

In alkaline carbonate solutions, hydrogen peroxide can selectively replace one of the carbonate ligands in UO2(CO3)3(4-) to form the ternary mixed U(VI) peroxo-carbonato species UO2(O2)(CO3)2(4-). Orange rectangular plates of K4[UO2(CO3)2(O2)].H2O were isolated and characterized by single crystal X-ray diffraction studies. Crystallographic data: monoclinic, space group P2(1)/ n, a = 6.9670(14) A, b = 9.2158(10) A, c = 18.052(4) A, Z = 4. Spectrophotometric titrations with H 2O 2 were performed in 0.5 M K 2CO 3, with UO2(O2)(CO3)2(4-) concentrations ranging from 0.1 to 0.55 mM. The molar absorptivities (M(-1) cm(-1)) for UO2(CO3)3(4-) and UO2(O2)(CO3)2(4-) were determined to be 23.3 +/- 0.3 at 448.5 nm and 1022.7 +/- 19.0 at 347.5 nm, respectively. Stoichiometric analyses coupled with spectroscopic comparisons between solution and solid state indicate that the stable solution species is UO2(O2)(CO3)2(4-), which has an apparent formation constant of log K' = 4.70 +/- 0.02 relative to the tris-carbonato complex.

The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO. [in fuel cells

NASA Technical Reports Server (NTRS)

Winnick, J.; Ross, P. N.

1980-01-01

The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

Reaction of silanes in supercritical CO2 with TiO2 and Al2O3.

PubMed

Gu, Wei; Tripp, Carl P

2006-06-20

Infrared spectroscopy was used to investigate the reaction of silanes with TiO2 and Al2O3 using supercritical CO2 (Sc-CO2) as a solvent. It was found that contact of Sc-CO2 with TiO2 leads to partial removal of the water layer and to the formation of carbonate, bicarbonate, and carboxylate species on the surface. Although these carbonate species are weakly bound to the TiO2 surface and can be removed by a N2 purge, they poison the surface, resulting in a lower level of reaction of silanes with TiO2. Specifically, the amount of hexamethyldisilazane adsorbed on TiO2 is about 10% of the value obtained when the reaction is performed from the gas phase. This is not unique to TiO2, as the formation of carbonate species also occurs upon contact of Al2O3 with Sc-CO2 and this leads to a lower level of reaction with hexamethyldisilazane. This is in contrast to reactions of silanes on SiO2 where Sc-CO2 has several advantages over conventional gaseous or nonaqueous methods. As a result, caution needs to be applied when using Sc-CO2 as a solvent for silanization reactions on oxides other than SiO2.

Synthesis and study of electronic state of Sr2CrO2Co2As2 with CoAs conduction layers

NASA Astrophysics Data System (ADS)

Suzuki, Atsushi; Ohta, Hiroto; Aruga Katori, Hiroko

2017-06-01

We successfully synthesized a new member of compounds with the CoAs layer, Sr2CrO2Co2As2, and its partially substituted systems Sr2CrO2(Tmx Co1- x )2As2 (Tm = Fe, Ni), and measured magnetization and electric resistivity of these polycrystalline compounds. As a result of magnetic measurement for Sr2CrO2Co2As2, magnetic moments of Co do not construct an itinerant electronic ferromagnetism unlike other compounds with the CoPn (Pn=P and As) layers. Both Sr2CrO2(Tmx Co1- x )2As2 with Tm = Fe and Ni also do not show an itinerant electronic ferromagnetism down to 2 K. For each solid solution of Sr2CrO2(Fe x Co1- x )2As2 with x > 0.0, ρ weakly increases with the decrease of T at low temperature region, indicating that the mixed occupancy of Cr and Fe within the conducting layers occurs in Sr2CrO2(Fe x Co1- x )2As2. We conclude that the absence of ferromagnetism in Sr2CrO2Co2As2 is due to the self-electron-doping from Cr to the conduction bands and the attempt to recover the ferromagnetism by the hole-doping effect is prevented by the mixed occupancy of Cr and Fe in Sr2CrO2 (Fe x Co1- x )2As2 with x > 0.0. The result of our structural analysis supports that the disappearance of itinerant electronic ferromagnetism in Sr2CrO2Co2As2 is due to the self-electron-doping from Cr.

Pt/SnO2-based CO-oxidation catalysts for CO2 lasers

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Schryer, David R.; Hess, Robert V.; Brown, Kenneth G.; Van Norman, John D.

1990-01-01

The activity of Pt/SnO2-based CO-oxidation catalysts has been maximized by optimizing pretreatment conditions and catalyst formulation. The role of H2O in activating these catalysts and of CO2 retention in deactivating them has been determined as has the interaction of these catalysts with rare-isotope C(0-18) and (O-18)2.

Integrated measurements and modeling of CO2, CH4, and N2O fluxes using soil microsite frequency distributions

NASA Astrophysics Data System (ADS)

Davidson, Eric; Sihi, Debjani; Savage, Kathleen

2017-04-01

Soil fluxes of greenhouse gases (GHGs) play a significant role as biotic feedbacks to climate change. Production and consumption of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are affected by complex interactions of temperature, moisture, and substrate supply, which are further complicated by spatial heterogeneity of the soil matrix. Models of belowground processes of these GHGs should be internally consistent with respect to the biophysical processes of gaseous production, consumption, and transport within the soil, including the contrasting effects of oxygen (O2) as either substrate or inhibitor. We installed automated chambers to simultaneously measure soil fluxes of CO2 (using LiCor-IRGA), CH4, and N2O (using Aerodyne quantum cascade laser) along soil moisture gradients at the Howland Forest in Maine, USA. Measured fluxes of these GHGs were used to develop and validate a merged model. While originally intended for aerobic respiration, the core structure of the Dual Arrhenius and Michaelis-Menten (DAMM) model was modified by adding M-M and Arrhenius functions for each GHG production and consumption process, and then using the same diffusion functions for each GHG and for O2. The area under a soil chamber was partitioned according to a log-normal probability distribution function, where only a small fraction of microsites had high available-C. The probability distribution of soil C leads to a simulated distribution of heterotrophic respiration, which translates to a distribution of O2 consumption among microsites. Linking microsite consumption of O2 with a diffusion model generates microsite concentrations of O2, which then determine the distribution of microsite production and consumption of CH4 and N2O, and subsequently their microsite concentrations using the same diffusion function. At many moisture values, there are some microsites of production and some of consumption for each gas, and the resulting simulated microsite concentrations of CH4

Comparative study on the effect of H2 pre-adsorption on CO oxidation in O2-poor atmosphere over Au/TiO2 and TiO2: Temperature programmed surface reaction by a multiplexed mass spectrometer testing

NASA Astrophysics Data System (ADS)

Si, Ruiru; Liu, Junfeng; Zhang, Yujuan; Chen, Xun; Dai, Wenxin; Fu, Xianzhi

2016-11-01

The behaviors of H2 pre-adsorption on CO oxidation in an O2-poor stream containing a trace H2O over Au/TiO2 and TiO2 have been investigated by a temperature programmed surface reaction testing, respectively. It was found that the H2 pre-adsorption could keep CO oxidation without H2O consumption over Au/TiO2, but suppress CO oxidation over TiO2. The chemisorption testing showed that the H2 adsorption at Au/TiO2 could benefit to the formation of Ti-bonded hydroxyl species (Ti4+-OH), while the H2 adsorption at TiO2 would consume the Ti-bonded hydroxyl species and form the bridge hydroxyl species (Ti4+-OH-Ti4+). These results show that only the Ti-bonded hydroxyl species (not all kinds of hydroxyl species) could act as the active species of oxidizing CO. Furthermore, it is suggested that the dissociative hydrogen adsorbed at Au sites could activate the lattice oxygen of TiO2 to form the active Ti-bonded hydroxyl species (hydrogen spillover from Au to TiO2), which exhibit a strong reducibility than the H directly adsorbed at TiO2.

Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

PubMed

Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

2014-07-17

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

Zeolites for CO2-CO-O2 Separation to Obtain CO2-Neutral Fuels.

PubMed

Perez-Carbajo, Julio; Matito-Martos, Ismael; Balestra, Salvador R G; Tsampas, Mihalis N; van de Sanden, Mauritius C M; Delgado, José A; Águeda, V Ismael; Merkling, Patrick J; Calero, Sofia

2018-06-20

Carbon dioxide release has become an important global issue due to the significant and continuous rise in atmospheric CO 2 concentrations and the depletion of carbon-based energy resources. Plasmolysis is a very energy-efficient process for reintroducing CO 2 into energy and chemical cycles by converting CO 2 into CO and O 2 utilizing renewable electricity. The bottleneck of the process is that CO remains mixed with O 2 and residual CO 2 . Therefore, efficient gas separation and recuperation are essential for obtaining pure CO, which, via water gas shift and Fischer-Tropsch reactions, can lead to the production of CO 2 -neutral fuels. The idea behind this work is to provide a separation mechanism based on zeolites to optimize the separation of carbon dioxide, carbon monoxide, and oxygen under mild operational conditions. To achieve this goal, we performed a thorough screening of available zeolites based on topology and adsorptive properties using molecular simulation and ideal adsorption solution theory. FAU, BRE, and MTW are identified as suitable topologies for these separation processes. FAU can be used for the separation of carbon dioxide from carbon monoxide and oxygen and BRE or MTW for the separation of carbon monoxide from oxygen. These results are reinforced by pressure swing adsorption simulations at room temperature combining adsorption columns with pure silica FAU zeolite and zeolite BRE at a Si/Al ratio of 3. These zeolites have the added advantage of being commercially available.

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

Preparation and photocatalytic properties of nanometer-sized magnetic TiO2/SiO2/CoFe2O4 composites.

PubMed

Li, Hansheng; Zhang, Yaping; Wu, Qin; Wang, Xitao; Liu, Changhao

2011-11-01

Magnetic TiO2/SiO2/CoFe2O4 nanoparticles (TiO2/SCFs) were prepared by a sol-gel process in a reverse microemulsion combined with solvent-thermal technique. TiO2/SCFs were characterized by Fourier transform infrared spectrometry, thermogravimetric analysis-differential scanning calorimetry, X-ray diffraction, Raman spectrometry, TEM, BET specific surface area measurement, and magnetic analysis. Structure analyses indicated that TiO2/SCFs presented a core-shell structure with TiO2 uniformly coating on SiO2/CoFe2O4 nanomagnets (SCFs) and typical ferromagnetic hysteresis. TiO2/SCFs showed larger specific surface area and better photocatalytic activities than TiO2 and TiO2/CoFe2O4 photocatalysts prepared by the same method. The doping interaction between TiO2 and CoFe2O4 reduced thanks to the inert SiO2 mesosphere.

Simultaneous Online Measurement of H2O and CO2 in the Humid CO2 Adsorption/Desorption Process.

PubMed

Yu, Qingni; Ye, Sha; Zhu, Jingke; Lei, Lecheng; Yang, Bin

2015-01-01

A dew point meter (DP) and an infrared (IR) CO2 analyzer were assembled in a humid CO2 adsorption/desorption system in series for simultaneous online measurements of H2O and CO2, respectively. The humidifier, by using surface-flushing on a saturated brine solution was self-made for the generation of humid air flow. It was found that by this method it became relatively easy to obtain a low H2O content in air flow and that its fluctuation could be reduced compared to the bubbling method. Water calibration for the DP-IR detector is necessary to be conducted for minimizing the measurement error of H2O. It demonstrated that the relative error (RA) for simultaneous online measurements H2O and CO2 in the desorption process is lower than 0.1%. The high RA in the adsorption of H2O is attributed to H2O adsorption on the transfer pipe and amplification of the measurement error. The high accuracy of simultaneous online measurements of H2O and CO2 is promising for investigating their co-adsorption/desorption behaviors, especially for direct CO2 capture from ambient air.

K-shell photoabsorption coefficients of O2, CO2, CO, and N2O

NASA Technical Reports Server (NTRS)

Barrus, D. M.; Blake, R. L.; Burek, A. J.; Chambers, K. C.; Pregenzer, A. L.

1979-01-01

The total photoabsorption coefficient has been measured from 500 to 600 eV around the K edge of oxygen in gases O2, CO2, CO, and N2O by means of a gold continuum source and crystal spectrometer with better than 1-eV resolution. The cross sections are dominated by discrete molecular-orbital transitions below the K-edge energy. A few Rydberg transitions were barely detectable. Broad shape resonances appear at or above the K edge. Additional broad, weak features above the K edge possibly arise from shake up. Quantitative results are given that have about 10% accuracy except on the very strong peaks. All the measured features are discussed in relation to other related measurements and theory.

Effects of addition of Bi2Ca2Co2O y on the thermoelectric properties of Ca3Co4O9 polycrystalline ceramics

NASA Astrophysics Data System (ADS)

Feng, Ningbo; Liao, Y. W.; Lu, Y.; He, Y.; Jin, Y. R.; Liu, X. R.

2018-06-01

Thermoelectric properties of Ca3Co4O9 polycrystalline ceramics with sheet grains were optimized by adding Bi2Ca2Co2O y phase. Therefore, the (1 - x) Ca3Co4O9/ x Bi2Ca2Co2O y (0 ≤ x ≤ 1) composites were prepared. The phase constitution and micro-structure of the samples were analyzed by XRD and SEM, respectively. With the addition of Bi2Ca2Co2O y , the apparent density D a and the relative density D r of the samples continuously increases. When x ≤ 0.4, the electrical resistivity of the samples declines, however, when x ≥ 0.4, the electrical resistivity of the samples increases. The Seebeck coefficient of the samples grows with the increase of the x monotonously. The power factor of the 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y samples reaches 0.24 mW m-1K-2 at 973 K. Thermal conductivity κ of the 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y monotonously decreases with the temperature rising, achieving the minimum about 1.34 W m-1K-1 at 973 K. The ZT of 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y composites gets to 0.18, which is comparable to that of most doped Ca3Co4O9 polycrystalline ceramics, implying higher ZT can be realized by combining the strategy of doping and introducing the Bi2Ca2Co2O y .

The causal link among militarization, economic growth, CO2 emission, and energy consumption.

PubMed

Bildirici, Melike E

2017-02-01

This paper examines the long-run and the causal relationship among CO 2 emissions, militarization, economic growth, and energy consumption for USA for the period 1960-2013. Using the bound test approach to cointegration, a short-run as well as a long-run relationship among the variables with a positive and a statistically significant relationship between CO 2 emissions and militarization was found. To determine the causal link, MWALD and Rao's F tests were applied. According to Rao's F tests, the evidence of a unidirectional causality running from militarization to CO 2 emissions, from energy consumption to CO 2 emissions, and from militarization to energy consumption all without a feedback was found. Further, the results determined that 26% of the forecast-error variance of CO 2 emissions was explained by the forecast error variance of militarization and 60% by energy consumption.

Co3(PO4)2·4H2O

PubMed Central

Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

2008-01-01

Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

La0.8Sr0.2Co0.8Ni0.2O3-δ impregnated oxygen electrode for H2O/CO2 co-electrolysis in solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Zheng, Haoyu; Tian, Yunfeng; Zhang, Lingling; Chi, Bo; Pu, Jian; Jian, Li

2018-04-01

High-temperature H2O/CO2 co-electrolysis through reversible solid oxide electrolysis cell (SOEC) provides potentially a feasible and eco-friendly way to convert electrical energy into chemicals stored in syngas. In this work, La0.8Sr0.2Co0.8Ni0.2O3-δ (LSCN) impregnated Gd0.1Ce0.9O1.95 (GDC)-(La0.8Sr0.2)0.95MnO3-δ (LSM) composite oxygen electrode is studied as high-performance electrode for H2O/CO2 co-electrolysis. The LSCN impregnated cell exhibits competitive performance with the peak power density of 1057 mW cm-2 at 800 °C in solid oxide fuel cell (SOFC) mode; in co-electrolysis mode, the current density can reach 1.60 A cm-2 at 1.5 V at 800 °C with H2O/CO2 ratio of 2/1. With LSCN nanoparticles dispersed on the surface of GDC-LSM to maximize the reaction active sites, the LSCN impregnated cell shows significant enhanced electrochemical performance at both SOEC and SOFC modes. The influence of feed gas composition (H2O-H2-CO2) and operating voltages on the performance of co-electrolysis are discussed in detail. The cell shows a very stable performance without obvious degradation for more than 100 h. Post-test characterization is analyzed in detail by multiple measurements.

Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

CoFe2O4-TiO2 and CoFe2O4-ZnO thin film nanostructures elaborated from colloidal chemistry and atomic layer deposition.

PubMed

Clavel, Guylhaine; Marichy, Catherine; Willinger, Marc-Georg; Ravaine, Serge; Zitoun, David; Pinna, Nicola

2010-12-07

CoFe(2)O(4)-TiO(2) and CoFe(2)O(4)-ZnO nanoparticles/film composites were prepared from directed assembly of colloidal CoFe(2)O(4) in a Langmuir-Blodgett monolayer and atomic layer deposition (ALD) of an oxide (TiO(2) or ZnO). The combination of these two methods permits the use of well-defined nanoparticles from colloidal chemistry, their assembly on a large scale, and the control over the interface between a ferrimagnetic material (CoFe(2)O(4)) and a semiconductor (TiO(2) or ZnO). Using this approach, architectures can be assembled with a precise control from the Angstrom scale (ALD) to the micrometer scale (Langmuir-Blodgett film). The resulting heterostructures present well-calibrated thicknesses. Electron microscopy and magnetic measurement studies give evidence that the size of the nanoparticles and their intrinsic magnetic properties are not altered by the various steps involved in the synthesis process. Therefore, the approach is suitable to obtain a layered composite with a quasi-monodisperse layer of ferrimagnetic nanoparticles embedded in an ultrathin film of semiconducting material.

The model of nano-scale copper particle removal from silicon surface in high pressure CO2 + H2O and CO2 + H2O + IPA cleaning solutions.

PubMed

Tan, Xin; Chai, Jiajue; Zhang, Xiaogang; Chen, Jiawei

2011-12-01

This study focuses on the description of the static forces in CO2-H2O and CO2-H2O-IPA cleaning solutions with a separate fluid phase entrapped between nano-scale copper particles and a silicon surface. Calculations demonstrate that increasing the pressure of the cleaning system decreases net adhesion force (NAF) between the particle and silicon. The NAF of a particle for in CO2-H2O-IPA system is less than that in CO2-H2O system, suggesting that the particles enter into bulk layer more easily as the CO2-H2O cleaning system is added IPA.

Neutron diffraction study of the inverse spinels Co2TiO4 and Co2SnO4

NASA Astrophysics Data System (ADS)

Thota, S.; Reehuis, M.; Maljuk, A.; Hoser, A.; Hoffmann, J.-U.; Weise, B.; Waske, A.; Krautz, M.; Joshi, D. C.; Nayak, S.; Ghosh, S.; Suresh, P.; Dasari, K.; Wurmehl, S.; Prokhnenko, O.; Büchner, B.

2017-10-01

We report a detailed single-crystal and powder neutron diffraction study of Co2TiO4 and Co2SnO4 between the temperature 1.6 and 80 K to probe the spin structure in the ground state. For both compounds the strongest magnetic intensity was observed for the (111)M reflection due to ferrimagnetic ordering, which sets in below TN=48.6 and 41 K for Co2TiO4 and Co2SnO4 , respectively. An additional low intensity magnetic reflection (200)M was noticed in Co2TiO4 due to the presence of an additional weak antiferromagnetic component. Interestingly, from both the powder and single-crystal neutron data of Co2TiO4 , we noticed a significant broadening of the magnetic (111)M reflection, which possibly results from the disordered character of the Ti and Co atoms on the B site. Practically, the same peak broadening was found for the neutron powder data of Co2SnO4 . On the other hand, from our single-crystal neutron diffraction data of Co2TiO4 , we found a spontaneous increase of particular nuclear Bragg reflections below the magnetic ordering temperature. Our data analysis showed that this unusual effect can be ascribed to the presence of anisotropic extinction, which is associated to a change of the mosaicity of the crystal. In this case, it can be expected that competing Jahn-Teller effects acting along different crystallographic axes can induce anisotropic local strain. In fact, for both ions Ti3 + and Co3 +, the 2 tg levels split into a lower dx y level yielding a higher twofold degenerate dx z/dy z level. As a consequence, one can expect a tetragonal distortion in Co2TiO4 with c /a <1 , which we could not significantly detect in the present work.

Analysis of the CO 2 Chemisorption in Li 5FeO 4, a New High Temperature CO 2 Captor Material. Effect of the CO 2 and O 2 Partial Pressures

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

Lara-García, Hugo A.; Sanchez-Camacho, Pedro; Duan, Yuhua

Pentalithium ferrite (Li 5FeO 4) was tested in this paper as possible CO 2 captor, both by theoretical calculations and experimental measurements. The pristine Li 5FeO 4 compound with orthorhombic structure was synthesized via solid-state reaction and it was structural and microstructurally characterized. Later, sample was heat-treated at temperatures from room temperature to 900 °C under different CO 2 or CO 2–O 2 atmospheres. Li 5FeO 4 exhibits excellent CO 2 chemisorption abilities with a capture capacity about 12.9 mmol/g, which is outstanding in comparison to other previously reported ceramic captors. This material is able to react with CO 2more » from 200 °C to approximately 715 °C showing a high kinetic of reaction even at CO 2 partial pressure values as low as 0.2. Finally and additionally, results suggest that oxygen addition does enhance the CO 2 chemisorption on Li 5FeO 4 at temperatures below 700 °C, although oxygen addition seems to favor the desorption process at higher temperatures.« less

Analysis of the CO 2 Chemisorption in Li 5FeO 4, a New High Temperature CO 2 Captor Material. Effect of the CO 2 and O 2 Partial Pressures

DOE PAGES

Lara-García, Hugo A.; Sanchez-Camacho, Pedro; Duan, Yuhua; ...

2017-01-23

Pentalithium ferrite (Li 5FeO 4) was tested in this paper as possible CO 2 captor, both by theoretical calculations and experimental measurements. The pristine Li 5FeO 4 compound with orthorhombic structure was synthesized via solid-state reaction and it was structural and microstructurally characterized. Later, sample was heat-treated at temperatures from room temperature to 900 °C under different CO 2 or CO 2–O 2 atmospheres. Li 5FeO 4 exhibits excellent CO 2 chemisorption abilities with a capture capacity about 12.9 mmol/g, which is outstanding in comparison to other previously reported ceramic captors. This material is able to react with CO 2more » from 200 °C to approximately 715 °C showing a high kinetic of reaction even at CO 2 partial pressure values as low as 0.2. Finally and additionally, results suggest that oxygen addition does enhance the CO 2 chemisorption on Li 5FeO 4 at temperatures below 700 °C, although oxygen addition seems to favor the desorption process at higher temperatures.« less

DFT study of CO2 and H2O co-adsorption on carbon models of coal surface.

PubMed

Gao, Zhengyang; Ding, Yi

2017-06-01

The moisture content of coal affects the adsorption capacity of CO 2 on the coal surface. Since the hydrogen bonds are formed between H 2 O and oxygen functional group, the H 2 O cluster more easily adsorbs on the coal micropore than CO 2 molecule. The coal micropores are occupied by H 2 O molecules that cannot provide extra space for CO 2 adsorption, which may leads to the reduction of CO 2 adsorption capacity. However, without considering factors of micropore and oxygen functional groups, the co-adsorption mechanisms of CO 2 and adsorbed H 2 O molecule are not clear. Density functional theory (DFT) calculations were performed to elucidate the effect of adsorbed H 2 O to CO 2 adsorption. This study reports some typical coal-H 2 O···CO 2 complexes, along with a detailed analysis of the geometry, energy, electrostatic potential (ESP), atoms in molecules (AIM), reduced density gradient (RDG), and energy decomposition analysis (EDA). The results show that H 2 O molecule can more stably adsorb on the aromatic ring surface than CO 2 molecule, and the absolute values of local ESP maximum and minimum of H 2 O cluster are greater than CO 2 . AIM analysis shows a detailed interaction path and strength between atoms in CO 2 and H 2 O, and RDG analysis shows that the interactions among CO 2 , H 2 O, and coal model belong to weak van der Waals force. EDA indicates that electrostatic and long-range dispersion terms play a primary role in the co-adsorption of CO 2 and H 2 O. According to the DFT calculated results without considering micropore structure and functional group, it is shown that the adsorbed H 2 O can promote CO 2 adsorption on the coal surface. These results demonstrate that the micropore factor plays a dominant role in affecting CO 2 adsorption capacity, the attractive interaction of adsorbed H 2 O to CO 2 makes little contribution.

Energetics of CO2 and H2O adsorption on zinc oxide.

PubMed

Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

2014-08-05

Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

Competitive Sorption of CO2 and H2O in 2:1 Layer Phyllosilicates

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

Schaef, Herbert T.; Loring, John S.; Glezakou, Vassiliki Alexandra

The salting out effect, where increasing the ionic strength of aqueous solutions decreases the solubility of dissolved gases is a well-known phenomenon. Less explored is the opposite process where an initially anhydrous system containing a volatile, relatively non-polar component and inorganic ions is systematically hydrated. Expandable clays such as montmorillonite are ideal systems for exploring this scenario as they have readily accessible exchange sites containing cations that can be systematically dehydrated or hydrated, from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO2 to bothmore » mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. Here, the partitioning of CO2 and H2O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO2 (scCO2) was investigated using in situ X-ray diffraction, infrared (IR)spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H2O and CO2 concentrations as a function of %H2O saturated in scCO2. Intercalation of CO2 is favored at low H2O/CO2 ratios in the interlayer region, where CO2 can solvate the interlayer cation. As the clay becomes more hydrated and the H2O/CO2 ratio increases, H2O displaces CO2 from the solvation shell of the cation and CO2 tends to segregate. This transition decreases both the entropic and enthalpic driving force for CO2 intercalation, consistent with experimentally observed loss of intercalated CO2.« less

Kinetics of Reduction of CaO-FeO x -MgO-PbO-SiO2 Slags by CO-CO2 Gas Mixtures

NASA Astrophysics Data System (ADS)

Jahanshahi, Sharif; Wright, Steven

2017-08-01

Kinetics of the reaction of lead slags (PbO-CaO-SiO2-FeO x -MgO) with CO-CO2 gas mixtures was studied by monitoring the changes in the slag composition when a stream of CO-CO2 gas mixture was blown on the surface of thin layers of slags (3 to 10 mm) at temperatures in the range of 1453 K to 1593 K (1180 °C to 1320 °C). These measurements were carried out under conditions where mass transfer in the gas phase was not the rate-limiting step and the reduction rates were insensitive to factors affecting mass transfer in the slag phase. The results show simultaneous reduction of PbO and Fe2O3 in the slag. The measured specific rate of oxygen removal from the melts varied from about 1 × 10-6 to 4 × 10-5 mol O cm-2 s-1 and was strongly dependent on the slag chemistry and its oxidation state, partial pressure of CO in the reaction gas mixture, and temperature. The deduced apparent first-order rate constant increased with increasing iron oxide content, oxidation state of the slag, and temperature. The results indicate that under the employed experimental conditions, the rate of formation of CO2 at the gas-slag interface is likely to be the rate-limiting step.

Mechanistic Study of CO 2 Photoreduction with H 2 O on Cu/TiO 2 Nanocomposites by in Situ X-ray Absorption and Infrared Spectroscopies

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

Liu, Lianjun; Zhao, Cunyu; Miller, Jeffrey T.

2016-12-15

Cu/TiO2 composites are extensively studied for photocatalytic reduction of CO2 with H2O, but the roles of Cu species (Cu2+, Cu+, or Cu0) is not well understood, and the photocatalyst deactivation mechanism is seldom addressed. In this work, we have employed in situ techniques, i.e., X-ray absorption spectroscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), to explore the surface chemistry of Cu/TiO2 composites under CO2 photoreduction environment. We found that the air-calcined Cu/TiO2 (Cu/Ti(air)) surface was dominated by isolated Cu2+ sites, while the one post-treated with H2 at 200 °C (Cu/Ti(H2)) was rich in Cu+ and oxygen vacancy (VO).more » Cu/Ti(H2) showed more than 50% higher activity than Cu/Ti(air) for CO2 photoreduction to CO, mainly resulting from the synergy of Cu+, OH groups, and VO that could scavenge holes to enhance electron transfer, provide CO2 adsorption sites, and facilitate the activation and conversion of the adsorbed CO2 (HCO3– and CO2–). Meanwhile, the consumption of OH groups and Cu+ active sites by holes may result in the deactivation of Cu/Ti(H2). Moreover, in situ XAS results directly demonstrated that (1) the photoinduced oxidation of Cu+ to Cu2+ changed the surrounding environments of Cu by increasing the coordination number; (2) thermal treatment by H2 could not fully recover the OH and Cu+ sites to their original states; and (3) adding hole scavengers (e.g., methanol) maintained or even increased the more active Cu+ species from the photoreduction of Cu2+, thus leading to a higher and more stable CO2 reduction activity. Findings in this work and the application of in situ XAS technique will help develop a more efficient photocatalyst for CO2 photoreduction and advance the understanding of the reaction mechanism and surface chemistry.« less

CO2 Sensors Based on Nanocrystalline SnO2 Doped with CuO

NASA Technical Reports Server (NTRS)

Xu, Jennifer C.; Hunter, Gary W.; Liu, Chung Chiun; Ward, Benjamin J.

2008-01-01

Nanocrystalline tin oxide (SnO2) doped with copper oxide (CuO) has been found to be useful as an electrical-resistance sensory material for measuring the concentration of carbon dioxide in air. SnO2 is an n-type semiconductor that has been widely used as a sensing material for detecting such reducing gases as carbon monoxide, some of the nitrogen oxides, and hydrocarbons. Without doping, SnO2 usually does not respond to carbon dioxide and other stable gases. The discovery that the electrical resistance of CuO-doped SnO2 varies significantly with the concentration of CO2 creates opportunities for the development of relatively inexpensive CO2 sensors for detecting fires and monitoring atmospheric conditions. This discovery could also lead to research that could alter fundamental knowledge of SnO2 as a sensing material, perhaps leading to the development of SnO2-based sensing materials for measuring concentrations of oxidizing gases. Prototype CO2 sensors based on CuO-doped SnO2 have been fabricated by means of semiconductor-microfabrication and sol-gel nanomaterial-synthesis batch processes that are amendable to inexpensive implementation in mass production.

Complexes in the Photocatalytic Reaction of CO2 and H2O: Theoretical Studies

PubMed Central

Luo, Dongmei; Zhang, Ning; Hong, Sanguo; Wu, Huanwen; Liu, Zhihua

2010-01-01

Complexes (H2O/CO2, e–(H2O/CO2) and h+–(H2O/CO2)) in the reaction system of CO2 photoreduction with H2O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H2O/CO2 captured photo-induced electron and hole produced e–(H2O/CO2) and h+–(H2O/CO2), respectively. The results revealed that CO2 and H2O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO2 and H2O, which might be attributed to the synergistic effect and which could not be captured experimentally. PMID:21152274

Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

NASA Astrophysics Data System (ADS)

Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

2018-02-01

Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.

Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

PubMed

Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-12-12

Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

'Design of CO-O2 recombination catalysts for closed-cycle CO2 lasers'

NASA Technical Reports Server (NTRS)

Guinn, K.; Goldblum, S.; Noskowski, E.; Herz, R.

1989-01-01

Pulsed CO2 lasers have many applications in aeronautics, space research, weather monitoring and other areas. Full exploitation of the potential of these lasers is hampered by the dissociation of CO2 that occurs during laser operation. The development of closed-cycle CO2 lasers requires active CO-O2 recombination (CO oxidation) catalysts and design methods for implementation of catalysts inside lasers. This paper will discuss the performance criteria and constraints involved in the design of monolith catalyst configurations for use in a closed-cycle laser and will present a design study performed with a computerized design program that had been written. Trade-offs between catalyst activity and dimensions, flow channel dimensions, pressure drop, O2 conversion and other variables will be discussed.

Spatially-controlled NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-01

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 Cores and MnO2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo2O4 and MnO2 compositions.

Spatially-controlled NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction.

PubMed

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-13

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo 2 O 4 @MnO 2 core-shell nanoarray with hollow NiCo 2 O 4 Cores and MnO 2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo 2 O 4 and MnO 2 compositions.

Solar kerosene from H2O and CO2

NASA Astrophysics Data System (ADS)

Furler, P.; Marxer, D.; Scheffe, J.; Reinalda, D.; Geerlings, H.; Falter, C.; Batteiger, V.; Sizmann, A.; Steinfeld, A.

2017-06-01

The entire production chain for renewable kerosene obtained directly from sunlight, H2O, and CO2 is experimentally demonstrated. The key component of the production process is a high-temperature solar reactor containing a reticulated porous ceramic (RPC) structure made of ceria, which enables the splitting of H2O and CO2 via a 2-step thermochemical redox cycle. In the 1st reduction step, ceria is endo-thermally reduced using concentrated solar radiation as the energy source of process heat. In the 2nd oxidation step, nonstoichiometric ceria reacts with H2O and CO2 to form H2 and CO - syngas - which is finally converted into kerosene by the Fischer-Tropsch process. The RPC featured dual-scale porosity for enhanced heat and mass transfer: mm-size pores for volumetric radiation absorption during the reduction step and μm-size pores within its struts for fast kinetics during the oxidation step. We report on the engineering design of the solar reactor and the experimental demonstration of over 290 consecutive redox cycles for producing high-quality syngas suitable for the processing of liquid hydrocarbon fuels.

Adsorption and reactions on a surface alloy: CO, NO, O 2 and CO 2 on Pd(100)-Mn-c(2×2)

NASA Astrophysics Data System (ADS)

Sandell, A.; Jaworowski, A. J.; Beutler, A.; Wiklund, M.

1999-02-01

The adsorption properties of the Pd(100)-Mn-c(2×2) surface alloy have been investigated using photoemission of both core and valence levels. CO adsorbs in a molecular form without affecting the alloy structure. Two CO species were found, one bonded to Pd, which desorbs upon heating to 270 K , and one bonded to Mn, which desorbs when heating to 400 K. O 2 destroys the alloy, leading to a disordered surface with MnO x complexes. The MnO x aggregates stabilize adsorbed CO 2 and act as active sites for the following oxidation reactions at 110 K: CO+O→CO 2, CO+2O→CO 3δ- and CO 2+O→CO 3δ-. The CO 2 species desorbs upon heating to 170 K , whereas the CO 3δ- species is stable up to temperatures between 300 and 500 K. When exposed to low amounts of NO at 110 K, the major part of the molecules dissociates in order to form MnO x, thereby destroying the alloy. Larger NO doses yield an increasing amount of molecular NO, which dissociate upon heating to 300 K. CO can react with the dissociated NO to form CO 2 and another species with a C 1s binding energy and thermal stability similar to that of CO 3δ-. This species was tentatively identified as -NCO or -NCO 2.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

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

Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

Mineralization of Basalts in the CO2-H2O-SO2-O2 System

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

Schaef, Herbert T.; Horner, Jacob A.; Owen, Antionette T.

2014-05-01

Sequestering carbon dioxide (CO2) containing minor amounts of co-contaminants in geologic formations was investigated in the laboratory through the use of high pressure static experiments. Five different basalt samples were immersed in water equilibrated with supercritical CO2 containing 1wt% sulfur dioxide (SO2) and 1wt% oxygen (O2) at reservoir conditions (~100 bar, 90°C) for 49 and 98 days. Gypsum (CaSO4) was a common precipitate, occurred early as elongated blades with striations, and served as substrates for other mineral products. Bimodal pulses of water released during dehydroxylation were key indicators along with X-ray diffraction for verifying the presences of jarosite-alunite group minerals.more » Well-developed pseudocubic jarosite crystals formed surface coatings, and in some instances mixtures of natrojarosite and natroalunite aggregated into spherically shaped structures measuring 100 μm in diameter. Reaction products were also characterized using infrared spectroscopy, which indicated OH and Fe-O stretching modes. The presences of jarosite-alunite group minerals were found in the lower wavenumber region from 700–400 cm-1. A strong preferential incorporation of Fe(III) into natrojarosite was attributed to the oxidation potential of O2. Evidence of CO2 was detected during thermal decomposition of precipitates, suggesting the onset of mineral carbonation.« less

Mineralization of basalts in the CO2-H2O-SO2-O2 system.

PubMed

Schaef, Herbert T; Horner, Jake A; Owen, Antoinette T; Thompson, Chris J; Loring, John S; McGrail, Bernard P

2014-05-06

Sequestering carbon dioxide (CO2) containing minor amounts of co-contaminants in geologic formations was investigated in the laboratory through the use of high pressure static experiments. Five different basalt samples were immersed in water equilibrated with supercritical CO2 containing 1 wt % sulfur dioxide (SO2) and 1 wt % oxygen (O2) at reservoir conditions (∼ 100 bar, 90 °C) for 48 and 98 days. Gypsum (CaSO4) was a common precipitate, occurred early as elongated blades with striations, and served as substrates for other mineral products. In addition to gypsum, bimodal pulses of water released during dehydroxylation were key indicators, along with X-ray diffraction, for verifying the presence of jarosite-alunite group minerals. Well-developed pseudocubic jarosite crystals formed surface coatings, and in some instances, mixtures of natrojarosite and natroalunite aggregated into spherically shaped structures measuring 100 μm in diameter. Reaction products were also characterized using infrared spectroscopy, which indicated OH and Fe-O stretching modes. The presences of jarosite-alunite group minerals were found in the lower wavenumber region from 700 to 400 cm(-1). A strong preferential incorporation of Fe(III) into natrojarosite was attributed to the oxidation potential of O2. Evidence of CO2 was detected during thermal decomposition of precipitates, suggesting the onset of mineral carbonation.

The effect of H2O and CO2 on planetary mantles

NASA Technical Reports Server (NTRS)

Wyllie, P. J.

1978-01-01

The peridotite-H2O-CO2 system is discussed, and it is shown that even traces of H2O and CO2, in minerals or vapor, lower mantle solidus temperatures through hundreds of degrees in comparison with the volatile-free solidus. The solidus for peridotite-H2O-CO2 is a divariant surface traversed by univariant lines that locate the intersections of subsolidus divariant surfaces for carbonation or hydration reactions occurring in the presence of H2O-CO2 mixtures. Vapor phase compositions are normally buffered to these lines, and near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus. Characteristics on the CO2 side of the maximum and on the H2O side of the maximum are described.

Theoretical study of the promotional effect of ZrO2 on In2O3 catalyzed methanol synthesis from CO2 hydrogenation

NASA Astrophysics Data System (ADS)

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2018-03-01

Methanol synthesis from CO2 hydrogenation on the ZrO2 doped In2O3(110) surface (Zr-In2O3(110)) with oxygen vacancy has been studied using the density functional theory calculations. The calculated results show that the doped ZrO2 species prohibits the excessive formation of oxygen vacancies and dissociation of H2 on In2O3 surface slightly, but enhances the adsorption of CO2 on both perfect and defective Zr-In2O3(110) surface. Methanol is formed via the HCOO route. The hydrogenation of CO2 to HCOO is both energetically and kinetically facile. The HCOO hydrogenates to polydentate H2CO (p-H2CO) species with an activation barrier of 0.75 eV. H3CO is produced from the hydrogenation of monodentate H2CO (mono-H2CO), transformation from p-H2CO with 0.82 eV reaction energy, with no barrier whether there is hydroxyl group between the mono-H2CO and the neighboring hydride or not. Methanol is the product of H3CO protonation with 0.75 eV barrier. The dissociation and protonation of CO2 are both energetically and kinetically prohibited on Zr-In2O3(110) surface. The doped ZrO2 species can further enhance the adsorption of all the intermediates involved in CO2 hydrogenation to methanol, activate the adsorbed CO2 and H2CO, and stabilize the HCOO, H2CO and H3CO, especially prohibit the dissociation of H2CO or the reaction of H2CO with neighboring hydride to form HCOO and gas phase H2. All these effects make the ZrO2 supported In2O3 catalyst exhibit higher activity and selectivity on methanol synthesis from CO2 hydrogenation.

Effect of H2O and CO2 on The Oxidation Behavior and Durability at High Temperature of ODS-FeCrAl

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

Dryepondt, Sebastien N; Rouaix-Vande Put, Aurelie; Pint, Bruce A

Cyclic oxidation testing was conducted on alloy MA956 and two different batches of alloy PM2000 at 1100 and 1200 C in different atmospheres rich in O2, H2O and CO2. Compare to 1h cycle in dry O2, exposure in air + 10 vol.% H2O resulted in an increase of the oxidation rate and a decrease of the time to breakaway for both alloys at 1200 C, and a faster consumption of Al in the MA956 alloy. 1h cyclic testing in 50%CO2/50%H2O+0.75% O2 had less of an impact on the oxidation rate but led to an increased formation of voids for alloymore » MA956, which had an impact on the alloy creep resistance. At 1100 C, exposure in 50%CO2/50%H2O resulted in significant oxide spallation compared with oxidation in air, but it was not the case when 0.75% O2 was added to the CO2/H2O mixture as a buffer. The control of impurities levels drastically improved the PM2000 oxidation resistance.« less

Effect of H2O and CO2 on The Oxidation Behavior and Durability at High Temperature of ODS-FeCrAl

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

Dryepondt, Sebastien N; Pint, Bruce A; Rouaix-Vande Put, Aurelie

Cyclic oxidation testing was conducted on alloy MA956 and two different batches of alloy PM2000 at 1100 and 1200 C in different atmospheres rich in O2, H2O and CO2. Compared to 1h cycles in dry O2, exposure in air+10 vol.% H2O resulted in an increase of the oxidation rate and a decrease of the time to breakaway for all alloys at 1200 C, and a faster consumption of Al in the MA956 alloy. One hour cyclic testing in 49.25%CO2+50%H2O+0.75% O2 had a smaller effect on the oxidation rate but led to increased formation of voids in alloy MA956, which hadmore » an impact on the alloy creep resistance. At 1100 C, exposure in 50%CO2+50%H2O resulted in significant oxide spallation compared with oxidation in air, but this was not the case when 0.75% O2 was added to the CO2/H2O mixture as a buffer. The control of impurity levels drastically improved the oxidation resistance of PM2000.« less

Detection of CO2 leaks from carbon capture and storage sites to the atmosphere with combined CO2 and O2 measurements

NASA Astrophysics Data System (ADS)

van Leeuwen, Charlotte; Meijer, Harro A. J.

2015-04-01

One of the main issues in carbon capture and storage (CCS) is the possibility of leakage of CO2 from the storage reservoir to the atmosphere, both from a public health and a climate change combat perspective. Detecting these leaks in the atmosphere is difficult due to the rapid mixing of the emitted CO2 with the surrounding air masses and the high natural variability of the atmospheric CO2 concentration. Instead of measuring only the CO2 concentration of the atmosphere, its isotopes or chemical tracers that are released together with the CO2, our method uses O2 measurements in addition to CO2 measurements to detect a leak from a CCS site. CO2 and O2 are coupled in most processes on earth. In photosynthesis, plants take up CO2 and release O2 at the same time. In respiration and fossil fuel burning, O2 is consumed while CO2 is released. In case of a leak from a CCS site, however, there is no relationship between CO2 and O2. A CO2 leak can therefore be distinguished from other sources of CO2 by looking at the atmospheric CO2-O2 ratio. A natural increase of the CO2 concentration is accompanied by a drop in the O2 concentration, while an increase in the CO2 concentration caused by a leak from a CCS site does not have any effect on the O2 concentration. To demonstrate this leak detection strategy we designed and built a transportable CO2 and O2 measurement system, that is capable of measuring the relatively minute (ppm's variations on a 21% concentration) changes in the O2 concentration. The system comprises of three cases that contain the instrumentation and gas handling equipment, the gas cylinders used as reference and calibration gases and a drying system, respectively. Air is pumped to the system from an air inlet that is placed in a small tower in the field. At the conference, we will demonstrate the success of leak detection with our system by showing measurements of several CO2 release experiments, where CO2 was released at a small distance from the air inlet of

Non-Potassic Melts In CMAS-CO2-H2O-K2O Model Peridotite

NASA Astrophysics Data System (ADS)

Buisman, I.; Walter, M. J.; Keshav, S.

2009-12-01

Volatile mediated model systems have been fundamental in shaping our knowledge about the way we view melting phase relations of peridotite at various depths in the Earth. Volatiles not only affect the melting temperatures, but the resulting liquids are, in some case, dramatically different than those witnessed in melting of dry peridotite. For example, the influence of CO2 and H2O on the melting phase relations of model peridotite shows a remarkable decrease in the solidus temperatures when compared to the dry peridotite (Gudfinnsson and Presnall, 2005). These model systems illustrate a gradational change above the solidus from carbonatites to kimberlites over several hundreds of degrees. Group-II kimberlites are ultrapotassic rocks with high water content where the mineral phlogopite is abundant. To get a better understanding of the melting phase relations related to carbonatitic and kimberlitic magmas, K2O was added to the system CMAS-CO2-H2O. In these systems, fluid and melt can co-exist in P-T space. However, from past studies, it is also known that in hydrous systems, both the fluid and melt will become indistinguishable from one another creating a singularity (second critical endpoint). Starting from the solidus located in six components (Keshav and Gudfinnsson, AGU abstract, 2009), with seven phases, melting phase relations in CMAS-CO2-H2O-K2O involving, fo-opx-cpx-garnet-carbonate-melt-fluid, are divariant. Fluid was recognized with the observation of large cavities seen in exposed capsules. Moreover, the presence of bright, needle-like grains found in large cavities in backscattered images implies the presence of solute in the fluid phase. Significantly, liquids on this divariant region have about 1000 ppm K2O, and so is the case with accompanying cpx. Hence, with this non-interesting amount of K2O in the mentioned phases, fluid must have all the potassium. At 30 kbar/1100C, with fo-opx-cpx-garnet-carbonate-phlogopite-melt-fluid, the melting phase

FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

PubMed

Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

2005-04-21

Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

Pressure, O2, and CO2, in aquatic Closed Ecological Systems

NASA Astrophysics Data System (ADS)

Taub, Frieda B.; McLaskey, Anna K.

2013-03-01

Pressure increased during net photosynthetic O2 production in the light and decreased during respiratory O2 uptake during the dark in aquatic Closed Ecological Systems (CESs) with small head gas volumes. Because most CO2 will be in the liquid phase as bicarbonate and carbonate anions, and CO2 is more soluble than O2, volumes of gaseous CO2 and gaseous O2 will not change in a compensatory manner, leading to the development of pressure. Pressure increases were greatest with nutrient rich medium with NaHCO3 as the carbon source. With more dilute media, pressure was greatest with NaHCO3, and less with cellulose or no-added carbon. Without adequate turbulence, pressure measurements lagged dissolved O2 concentrations by several hours and dark respiration would have been especially underestimated in our systems (250-1000 ml). With adequate turbulence (rotary shaker), pressure measurements and dissolved O2 concentrations generally agreed during lights on/off cycles, but O2 measurements provided more detail. At 20 °C, 29.9 times as much O2 will distribute into the gas phase as in the liquid, per unit volume, as a result of the limited solubility of O2 in water and according to Henry's Law. Thus even a small head gas volume can contain more O2 than a larger volume of water. When both dissolved and gaseous O2 and CO2 are summed, the changes in Total O2 and CO2 are in relatively close agreement when NaHCO3 is the carbon source. These findings disprove an assumption made in some of Taub's earlier research that aquatic CESs would remain at approximately atmospheric pressure because approximately equal molar quantities of O2 and CO2 would exchange during photosynthesis and respiration; this assumption neglected the distribution of O2 between water and gas phases. High pressures can occur when NaHCO3 is the carbon source in nutrient rich media and if head-gas volumes are small relative to the liquid volume; e.g., one "worse case" condition developed 800 mm Hg above atmospheric

Nano-crystalline phase evolution and structural modification in Co/V substituted Li2O-Bi2O3-B2O3 glasses

NASA Astrophysics Data System (ADS)

Yadav, Arti; Dahiya, M. S.; Hooda, A.; Agarwal, A.; Khasa, S.

2018-05-01

Co/V substituted Li2O-Bi2O3-B2O3 glasses having composition 7CoO•23Li2O•20Bi2O3•50B2O3(CLBB) and xCoO•(30-x)Li2O•20Bi2O3•50B2O3(x = 0.0, 2.0, 5.0, 7.0 and 10.0 mol%, CVLBB1-5 respectively) developed via melt- quench route. The effect of annealing on structural properties of prepared samples was investigated by using XRD patterns and FTIR spectroscopy. Glasses annealed at 400˚C remained amorphous whereas glasses annealed at 500˚C changes from glasses to glass ceramics. The different crystalline phases i.e. Bi2(V0.9Co0.1)O5.25, LiCoVO4, V2O5 & Bi2(VO5) evolve on annealing at 500°C for 6 hours confirmed from the corresponding XRD patterns. The crystallite size of prepared samples were found to vary as 38-60nm This indicated that CoO and V2O5 introduced in matrix act as crystallizing agents and cause structural modification as studied by the FTIR spectra for all heat treated compositions.

O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

PubMed

Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

2017-10-05

Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

Synthesis of magnetic Bi2O2CO3/ZnFe2O4 composite with improved photocatalytic activity and easy recyclability

NASA Astrophysics Data System (ADS)

Liu, Yumin; Ren, Hao; Lv, Hua; Guang, Jing; Cao, Yafei

2018-03-01

Magnetic Bi2O2CO3/ZnFe2O4 heterojunction photocatalysts with varying content of ZnFe2O4 were constructed by modifying Bi2O2CO3 nanosheets with mesoporous ZnFe2O4 nanoparticles. The photoactivity of the products was investigated by decomposing RhodamineB (RhB) and it was found that the photoactivity of Bi2O2CO3/ZnFe2O4 composite was closely related to the loading amount of ZnFe2O4. Under simulant sunlight irradiation, the optimum photoactivity of Bi2O2CO3/ZnFe2O4 composite was almost 2.3 and 2.1 times higher than that by bare ZnFe2O4 and Bi2O2CO3, respectively. The improved photoactivity resulted from the synergistic effect of Bi2O2CO3 and ZnFe2O4, which not only extended the photoabsorption region but also significantly facilitated the interfacial charge transfer. Besides the high photocatalytic performance, Bi2O2CO3/ZnFe2O4 composite also exhibited excellent stable and recycling properties, which enabled it have great potential in a long-term practical use.

Core/shell structure NiCo2O4@MnCo2O4 nanofibers fabricated by different temperatures for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Qing; Qin, Xuefeng; Jiang, Pengcheng; Dai, Jianfeng; Li, Weixue; Gao, Haoran

2018-03-01

Core/shell structure NiCo2O4@MnCo2O4 nanofibers (NiCo2O4@MnCo2O4 NFs) were prepared by a facile co-electrospinning method and heat treatment. The composites annealed at 500 °C have a complete, continuously obvious core/shell structure, and clear interface of composites with good morphology, while annealed at 600 °C were stacked on each other and were unable to sustain three-dimensional network structures and 700 °C calcination have completely lost one-dimensional structure. The core NiCo2O4 is about 70 nm in diameter and the MnCo2O4 shell behaves a thickness about 60 nm. When investigated as an electrode material for supercapacitors, the NiCo2O4@MnCo2O4 NFs annealed at 500 °C exihibited the specific capacitance of 463 F g-1 (0.926 F cm-2) at 1 A g-1, higher than that annealed at 600 °C 362 F g-1, 1 A g-1 (0.724 F cm-2, 1 A g-1) and 700 °C 283 F g-1, 1 A g-1 (0.566 F cm-2, 1 A g-1). These results suggest that core/shell NiCo2O4@MnCo2O4 NFs annealed at 500 °C have formed a good morphology with continuously complete core/shell structure which lead to good properties would be potential electrodes for supercapacitors.

Microwave spectroscopy of the seeded binary and ternary clusters CO-(pH{sub 2}){sub 2}, CO-pH{sub 2}-He, CO-HD, and CO-(oD{sub 2}){sub N=1,2}

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

Raston, Paul L., E-mail: paul.raston@adelaide.edu.au; Jäger, Wolfgang

We report the Fourier transform microwave spectra of the a-type J = 1-0 transitions of the binary and ternary CO-(pH{sub 2}){sub 2}, CO-pH{sub 2}-He, CO-HD, and CO-(oD{sub 2}){sub N=1,2} clusters. In addition to the normal isotopologue of CO for all clusters, we observed the transitions of the minor isotopologues, {sup 13}C{sup 16}O, {sup 12}C{sup 18}O, and {sup 13}C{sup 18}O, for CO-(pH{sub 2}){sub 2} and CO-pH{sub 2}-He. All transitions lie within 335 MHz of the experimentally or theoretically predicted values. In comparison to previously reported infrared spectra [Moroni et al., J. Chem. Phys. 122, 094314 (2005)], we are able to tentativelymore » determine the vibrational shift for CO-pH{sub 2}-He, in addition to its b-type J = 1-0 transition frequency. The a-type frequency of CO-pH{sub 2}-He is similar to that of CO-He{sub 2} [Surin et al., Phys. Rev. Lett. 101, 233401 (2008)], suggesting that the pH{sub 2} molecule has a strong localizing effect on the He density. Perturbation theory analysis of CO-oD{sub 2} reveals that it is approximately T-shaped, with an anisotropy of the intermolecular potential amounting to ∼9 cm{sup −1}.« less

Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability.

PubMed

Liu, Lianjun; Zhao, Cunyu; Zhao, Huilei; Pitts, Daniel; Li, Ying

2013-05-07

A novel MgO-patched TiO2 microsphere photocatalyst demonstrated 10 times higher activity toward CO production from CO2 photoreduction with H2O vapor, when the reaction temperature increased from 50 to 150 °C. The catalytic performance of hybrid MgO-TiO2 was much more stable than TiO2, particularly at a higher temperature, likely due to easier desorption of reaction intermediates and the enhanced CO2 adsorption by MgO.

Evaluation of the impact of H2O, O2, and SO2 on postcombustion CO2 capture in metal-organic frameworks.

PubMed

Yu, Jiamei; Ma, Yuguang; Balbuena, Perla B

2012-05-29

Molecular modeling methods are used to estimate the influence of impurity species: water, O(2), and SO(2) in flue gas mixtures present in postcombustion CO(2) capture using a metal organic framework, HKUST-1, as a model sorbent material. Coordinated and uncoordinated water effects on CO(2) capture are analyzed. Increase of CO(2) adsorption is observed for both cases, which can be attributed to the enhanced binding energy between CO(2) and HKUST-1 due to the introduction of a small amount of water. Density functional theory calculations indicate that the binding energy between CO(2) and HKUST-1 with coordinated water is ~1 kcal/mol higher than that without coordinated water. It is found that the improvement of CO(2)/N(2) selectivity induced by coordinated water may mainly be attributed to the increased CO(2) adsorption on the hydrated HKUST-1. On the other hand, the enhanced selectivity induced by uncoordinated water in the flue gas mixture can be explained on the basis of the competition of adsorption sites between water and CO(2) (N(2)). At low pressures, a significant CO(2)/N(2) selectivity increase is due to the increase of CO(2) adsorption and decrease of N(2) adsorption as a consequence of competition of adsorption sites between water and N(2). However, with more water molecules adsorbed at higher pressures, the competition between water and CO(2) leads to the decrease of CO(2) adsorption capacity. Therefore, high pressure operation should be avoided in HKUST-1 sorbents for CO(2) capture. In addition, the effects of O(2) and SO(2) on CO(2) capture in HKUST-1 are investigated: The CO(2)/N(2) selectivity does not change much even with relatively high concentrations of O(2) in the flue gas (up to 8%). A slightly lower CO(2)/N(2) selectivity of a CO(2)/N(2)/H(2)O/SO(2) mixture is observed compared with that in a CO(2)/N(2)/H(2)O mixture, especially at high pressures, due to the strong SO(2) binding with HKUST-1.

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.

Mitigating climate change through the understanding of Nitrous Oxide (N2O) consumption processes in peat lands

NASA Astrophysics Data System (ADS)

Akrami, N.; Barker, X. Z.; Horwath, W. R.

2017-12-01

Nitrous Oxide (N2O) with global warming potential of 298 over a 100-year horizon is one of the most potent green house gases. In the United States, agriculture share to N2O emissions is over 70%. Peat lands, however, are being considered as both sources and sinks of greenhouse gases. N2O emissions are a product of both production and consumption processes. However, there is still a lack of understanding of N2O consumption processes in soils. In this work, the potential of re-wetted peat lands planted to rice in Sacramento-San Joaquin Delta, California, to act as a potential sink for N2O is being evaluated. Four peat land soils with 1%, 5%, 11% and 23% of organic carbon have been anaerobically incubated with different water contents (15%, 30%, 50%, 75% and 100% of their water holding capacity). 15N-N2O gas has been injected to the headspace of experiment jars and the production and consumption rate of 15N-N2O, 15N-N2 and production rate of Carbon Dioxide (CO2) and Methane (CH4) along with dissolved Nitrate (NO3-), Nitrite (NO2-), Ammonium (NH4+), Iron (II) and Iron (III) concentration has been quantified. Our results show promising N2O consumption rates under high carbon content and relatively high water content treatments. This research introduces organic carbon and water content as two major criteria in N2O consumption processes in peat lands that make it a potential hotspot for climate changes mitigation through adopting effective management practices to decrease greenhouse gas emissions.

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.

The effect of Fe2O3 crystal phases on CO2 hydrogenation

PubMed Central

Wang, Tianqi; Chen, Hongxian; Yang, Xiazhen; Jin, Yangfu

2017-01-01

The effect of Fe2O3 crystal phases on their performance in CO2 hydrogenation was studied. α-Fe2O3 crystal was prepared by precipitation method from Fe(NO3)3·9H2O and (NH4)2CO3, and γ-Fe2O3 was prepared by grinding Fe(NO3)3·9H2O and L(+)-Tartaric acid in agate mortar completely. The crystal phases of Fe2O3 influence the distribution of promoter Zn, K and Cu on catalysts. The dispersity of K on γ-Fe2O3 surface is higher than α-Fe2O3. On the contrary, Cu and Zn are more dispersive on α-Fe2O3 surface than γ-Fe2O3. The catalyst in γ-Fe2O3 phase is easily reduced relative to the catalyst in α-Fe2O3 phase. The former presents higher CO2 conversion and C2+ hydrocarbon selectivity than the latter in CO2 hydrogenation. PMID:28806421

The effect of Fe2O3 crystal phases on CO2 hydrogenation.

PubMed

Ning, Wensheng; Wang, Tianqi; Chen, Hongxian; Yang, Xiazhen; Jin, Yangfu

2017-01-01

The effect of Fe2O3 crystal phases on their performance in CO2 hydrogenation was studied. α-Fe2O3 crystal was prepared by precipitation method from Fe(NO3)3·9H2O and (NH4)2CO3, and γ-Fe2O3 was prepared by grinding Fe(NO3)3·9H2O and L(+)-Tartaric acid in agate mortar completely. The crystal phases of Fe2O3 influence the distribution of promoter Zn, K and Cu on catalysts. The dispersity of K on γ-Fe2O3 surface is higher than α-Fe2O3. On the contrary, Cu and Zn are more dispersive on α-Fe2O3 surface than γ-Fe2O3. The catalyst in γ-Fe2O3 phase is easily reduced relative to the catalyst in α-Fe2O3 phase. The former presents higher CO2 conversion and C2+ hydrocarbon selectivity than the latter in CO2 hydrogenation.

Carbon dioxide consumption of the microalga Scenedesmus obtusiusculus under transient inlet CO2 concentration variations.

PubMed

Cabello, Juan; Morales, Marcia; Revah, Sergio

2017-04-15

The extensive microalgae diversity offers considerable versatility for a wide range of biotechnological applications in environmental and production processes. Microalgal cultivation is based on CO 2 fixation via photosynthesis and, consequently, it is necessary to evaluate, in a short time and reliable way, the effect of the CO 2 gas concentration on the consumption rate and establish the tolerance range of different strains and the amount of inorganic carbon that can be incorporated into biomass in order to establish the potential for industrial scale application. Dynamic experiments allow calculating the short-term microalgal photosynthetic activity of strains in photobioreactors. In this paper, the effect of step-changes in CO 2 concentration fed to a 20L bubble column photobioreactor on the CO 2 consumption rate of Scenedesmus obtusiusculus was evaluated at different operation times. The highest apparent CO 2 consumption rate (336μmolm -2 s -1 and 5.6% of CO 2 ) was 6530mg CO2 g b -1 d -1 and it decreased to 222mg CO2 g b -1 d -1 when biomass concentration increased of 0.5 to 3.1g b L -1 and 5.6% of CO 2 was fed. For low CO 2 concentrations (<3.8%) the pH remained close to the optimal value (7.5 and 8). The CO 2 consumption rates show that S. obtusiusculus was not limited by CO 2 availability for concentrations above of 3.8%. The CO 2 mass balance showed that 90% of the C-CO 2 transferred was used for S. obtusiusculus growth. Copyright © 2017. Published by Elsevier B.V.

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

PubMed

Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

2018-03-27

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all

Effects of N2-O2 and CO2-O2 tensions on growth of fungi isolated from damaged flue-cured tobacco.

PubMed

Yang, H; Lucas, G B

1970-02-01

Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N(2)-O(2) or CO(2)-O(2). A 1 to 5% concentration of O(2) in an N(2) atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O(2) for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O(2). High O(2) concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O(2) in the N(2) atmosphere, furrows formed in mycelial mats between 5 and 40% O(2) in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O(2) decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO(2)-O(2) mixtures radial growth of all species increased with each quantitative decrease of CO(2). All species except A. niger grew faster in air than in 10% CO(2). In contrast to N(2)-O(2) mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O(2) concentrations.

Reactions of hydrated electrons (H2O)n- with carbon dioxide and molecular oxygen: hydration of the CO2- and O2- ions.

PubMed

Balaj, O Petru; Siu, Chi-Kit; Balteanu, Iulia; Beyer, Martin K; Bondybey, Vladimir E

2004-10-04

The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

Electrochemical CO2 and O2 separation for crew and plant environments

NASA Technical Reports Server (NTRS)

Lee, M. G.; Grigger, David J.; Foerg, Sandra L.

1992-01-01

The study describes a closed ecosystem concept that includes electrochemical CO2 and O2 separators and a moisture condenser/separator for maintaining CO2, O2, and humidity levels in the crew and plant habitats at their respective optimal conditions. The key processes of this concept are aqueous electrolyte-based electrochemical CO2 and O2 separations. The principles and cell characteristics of these electrochemical gas separation processes are described. Also presented are descriptions of test hardware and the test results of the Electrochemical CO2 Separator (ECS) and the Electrochemical O2 Separator (EOS), and the combination of the ECS and the EOS. The test results proved that the ECS and EOS processes for the combined concept are viable.

Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

PubMed

Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

2015-01-01

The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

NASA Technical Reports Server (NTRS)

Brown, L. R.; Toth, R. A.

1985-01-01

The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

Ignition and Combustion of Pulverized Coal and Biomass under Different Oxy-fuel O2/N2 and O2/CO2 Environments

NASA Astrophysics Data System (ADS)

Khatami Firoozabadi, Seyed Reza

This work studied the ignition and combustion of burning pulverized coals and biomasses particles under either conventional combustion in air or oxy-fuel combustion conditions. Oxy-fuel combustion is a 'clean-coal' process that takes place in O2/CO2 environments, which are achieved by removing nitrogen from the intake gases and recirculating large amounts of flue gases to the boiler. Removal of nitrogen from the combustion gases generates a high CO2-content, sequestration-ready gas at the boiler effluent. Flue gas recirculation moderates the high temperatures caused by the elevated oxygen partial pressure in the boiler. In this study, combustion of the fuels took place in a laboratory laminar-flow drop-tube furnace (DTF), electrically-heated to 1400 K, in environments containing various mole fractions of oxygen in either nitrogen or carbon-dioxide background gases. The experiments were conducted at two different gas conditions inside the furnace: (a) quiescent gas condition (i.e., no flow or inactive flow) and, (b) an active gas flow condition in both the injector and furnace. Eight coals from different ranks (anthracite, semi-snthracite, three bituminous, subbituminous and two lignites) and four biomasses from different sources were utilized in this work to study the ignition and combustion characteristics of solid fuels in O2/N2 or O2/CO2 environments. The main objective is to study the effect of replacing background N2 with CO2, increasing O2 mole fraction and fuel type and rank on a number of qualitative and quantitative parameters such as ignition/combustion mode, ignition temperature, ignition delay time, combustion temperatures, burnout times and envelope flame soot volume fractions. Regarding ignition, in the quiescent gas condition, bituminous and sub-bituminous coal particles experienced homogeneous ignition in both O2/N 2 and O2/CO2 atmospheres, while in the active gas flow condition, heterogeneous ignition was evident in O2/CO 2. Anthracite, semi

Energy transfer mechanism of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors

NASA Astrophysics Data System (ADS)

Prasad, V. Reddy; Damodaraiah, S.; Ratnakaram, Y. C.

2018-04-01

Sm3+/Eu3+ co-doped calcium borophosphate phosphors were synthesized by solid state reaction method. 2CaO-B2O3-P2O5: Sm3+/Eu3+ co-doped phosphors were characterized by XRD, SEM, 31P solid state NMR, excitation, photoluminescence (PL) and decay profiles.. XRD profiles showed that the prepared phosphors exhibit a hexagonal phase in crystal structure and SEM results showed that the particles are more irregular morphologies. From 31P NMR spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors, the chemical shifts located in the positive frequency region indicating the presence of mono-phosphate complexes Q0-(PO43 - ) . Photoluminescence spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors show enhancement in emission intensity of Eu3+ ion due to co-doping with Sm3+ ions through energy transfer process. The energy level mechanism between Sm3+ and Eu3+ ions has been clearly explained. The energy transfer process has also been evidenced by lifetime decay profiles. These results suggest that the prepared phosphors are potential red luminescent optical materials.

Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

PubMed

Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

2015-08-14

The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

Microbial CH4 and N2O Consumption in Acidic Wetlands

PubMed Central

Kolb, Steffen; Horn, Marcus A.

2012-01-01

Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4), and nitrous oxide (N2O). Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots). Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and denitrifiers that consume atmospheric CH4 and N2O in acidic wetlands. PMID:22403579

Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

PubMed

Ko, Young Gun; Shin, Seung Su; Choi, Ung Su

2011-09-15

CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket". Copyright © 2011. Published by Elsevier Inc.

China's transportation energy consumption and CO2 emissions from a global perspective

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

Yin, Xiang; Chen, Wenying; Eom, Jiyong

2015-07-01

ABSTRACT Rapidly growing energy demand from China's transportation sector in the last two decades have raised concerns over national energy security, local air pollution, and carbon dioxide (CO2) emissions, and there is broad consensus that China's transportation sector will continue to grow in the coming decades. This paper explores the future development of China's transportation sector in terms of service demands, final energy consumption, and CO2 emissions, and their interactions with global climate policy. This study develops a detailed China transportation energy model that is nested in an integrated assessment model—Global Change Assessment Model (GCAM)—to evaluate the long-term energy consumptionmore » and CO2 emissions of China's transportation sector from a global perspective. The analysis suggests that, without major policy intervention, future transportation energy consumption and CO2 emissions will continue to rapidly increase and the transportation sector will remain heavily reliant on fossil fuels. Although carbon price policies may significantly reduce the sector's energy consumption and CO2 emissions, the associated changes in service demands and modal split will be modest, particularly in the passenger transport sector. The analysis also suggests that it is more difficult to decarbonize the transportation sector than other sectors of the economy, primarily owing to its heavy reliance on petroleum products.« less

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

PubMed

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-27

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

VUV photoionization cross sections of HO2, H2O2, and H2CO.

PubMed

Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

2015-02-26

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria.

PubMed

Chueh, William C; Falter, Christoph; Abbott, Mandy; Scipio, Danien; Furler, Philipp; Haile, Sossina M; Steinfeld, Aldo

2010-12-24

Because solar energy is available in large excess relative to current rates of energy consumption, effective conversion of this renewable yet intermittent resource into a transportable and dispatchable chemical fuel may ensure the goal of a sustainable energy future. However, low conversion efficiencies, particularly with CO(2) reduction, as well as utilization of precious materials have limited the practical generation of solar fuels. By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO(2) and H(2)O, yielding CO and H(2), respectively. Stable and rapid generation of fuel was demonstrated over 500 cycles. Solar-to-fuel efficiencies of 0.7 to 0.8% were achieved and shown to be largely limited by the system scale and design rather than by chemistry.

Effects of N2-O2 and CO2-O2 Tensions on Growth of Fungi Isolated from Damaged Flue-Cured Tobacco 1

PubMed Central

Yang, H.; Lucas, G. B.

1970-01-01

Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N2-O2 or CO2-O2. A 1 to 5% concentration of O2 in an N2 atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O2 for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O2. High O2 concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O2 in the N2 atmosphere, furrows formed in mycelial mats between 5 and 40% O2 in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O2 decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO2-O2 mixtures radial growth of all species increased with each quantitative decrease of CO2. All species except A. niger grew faster in air than in 10% CO2. In contrast to N2-O2 mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O2 concentrations. PMID:5461786

Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

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

Neary, Michelle C.; Parkin, Gerard

Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe3)(CO)2H, CpMo(PMe3)2(CO)H, [CpMo(μ-O)(μ-O2CH)]2, and [Cp*Mo(μ-O)(μ-O2CH)]2.

PubMed

Neary, Michelle C; Parkin, Gerard

2017-02-06

The molecular structures of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H 2 from formic acid, the carbonyl derivatives, Cp R Mo(CO) 3 H, are also observed to form dinuclear formate compounds, namely, [Cp R Mo(μ-O)(μ-O 2 CH)] 2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2 CH)] 2 and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2 CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ 2 δ* 2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

DOE PAGES

Neary, Michelle C.; Parkin, Gerard

2017-01-19

Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

O2(a1Δ) quenching in O/O2/O3/CO2/He/Ar mixtures

NASA Astrophysics Data System (ADS)

Azyazov, V. N.; Mikheyev, P. A.; Postell, D.; Heaven, M. C.

2010-02-01

The development of discharge singlet oxygen generators (DSOG's) that can operate at high pressures is required for the power scaling of the discharge oxygen iodine laser. In order to achieve efficient high-pressure DSOG operation it is important to understand the mechanisms by which singlet oxygen (O2(a1Δ)) is quenched in these devices. It has been proposed that three-body deactivation processes of the type O2(a1Δ))+O+M-->2O2+M provide significant energy loss channels. To further explore these reactions the physical and reactive quenching of O2(a1Δ)) in O(3P)/O2/O3/CO2/He/Ar mixtures has been investigated. Oxygen atoms and singlet oxygen molecules were produced by the 248 nm laser photolysis of ozone. The kinetics of O2(a1Δ)) quenching were followed by observing the 1268 nm fluorescence of the O2 a1Δ-X3Ε transition. Fast quenching of O2(a1Δ)) in the presence of oxygen atoms and molecules was observed. The mechanism of the process has been examined using kinetic models, which indicate that quenching by vibrationally excited ozone is the dominant reaction.

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols.

PubMed

Bi, Jianhong; Kong, Lingtao; Huang, Zixiang; Liu, Jinhuai

2008-06-02

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.

Photoreduction of CO2 on TiO2/SrTiO3 Heterojunction Network Film

NASA Astrophysics Data System (ADS)

Bi, Yongsheng; Zong, Lanlan; Li, Chen; Li, Qiuye; Yang, Jianjun

2015-08-01

Nanotube titanic acid (NTA) network film has a porous structure and large BET surface area, which lead them to possessing high utilization of the incident light and strong adsorption ability. We used NTA as the precursor to fabricate a TiO2/ SrTiO3 heterojunction film by the hydrothermal method. In the process of the reaction, part of NTA reacted with SrCl2 to form SrTiO3 nanocubes, and the remainder dehydrated to transform to the rutile TiO2. The ratio of TiO2 and SrTiO3 varied with the hydrothermal reaction time. SEM and TEM images indicated that SrTiO3 nanocubes dispersed uniformly on TiO2 film, and the particle size and crystallinity of SrTiO3 nanocubes increased with the reaction time prolonging. The TiO2/SrTiO3 heterojunction obtained by 1 h showed the best activity for CO2 photoreduction, where the mole ratio of TiO2 and SrTiO3 was 4:1. And the photo-conversion efficiency of CO2 to CH4 improved remarkably after the foreign electron traps of Pt and Pd nanoparticles were loaded. The highest photocatalytic production rate of CH4 reached 20.83 ppm/h cm2. In addition, the selectivity of photoreduction product of CO2 was also increased apparently when Pd acted as the cocatalyst on TiO2/SrTiO3 heterojunction film.

Conductivity measurements on H 2O-bearing CO 2-rich fluids

DOE PAGES

Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; ...

2014-09-10

Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H 2O to CO 2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO 2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H 2O concentrationsmore » up to ~1600 ppmw (xH 2O ≈ 3.9 x 10 -3), corresponding to the H 2O solubility limit in liquid CO 2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO 2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

Coupling of N2O and CO2 fluxes from agriculture in Michigan

NASA Astrophysics Data System (ADS)

Cui, M.; Tang, J.; Hastings, M. G.; Gelfand, I.; Tao, L.; Sun, K.

2012-12-01

CO2 has been known to cause global warming, and N2O is the largest contributor to the greenhouse gas burden of cropping systems in the United States due to application of fertilizer. In our study, fluxes of N2O and CO2 were measured at two maize fields and one reference grassland from Kellogg Biological Station in Southwest Michigan. Here we compared two measuring systems, traditional GC method and LGR/Li-Cor system. Our initial results show that the two measuring systems are consistent (N2O slope=0.96, R2=0.96; and CO2 slope= 1.03, R2=0.86 measuring from the same chamber). Measurements done in pairs of chambers suggest great spatial variations, despite that the chambers were only 0.5 meter apart. The two systems are still comparable by averaging 8 pairs of chambers distributed within one site. Increase of CO2 fluxes were observed the second day after fertilization, but no significant change of N2O fluxes was shown. After artificial rainfall, boosting N2O fluxes and further increase in CO2 fluxes were demonstrated. Our result indicates that precipitation is necessary before a prominent N2O peak. In our LGR/Li-Cor system, CO was also measured from chambers. Interesting CO fluxes were shown in our experiment. Soil, which is usually considered as a CO sink, emits CO in some chambers during our measurement, which is probably related to the nationwide forest fires and lack of precipitation during the period.

Water inhibits CO oxidation on gold cations in the gas phase. Structures and binding energies of the sequential addition of CO, H2O, O2, and N2 onto Au.

PubMed

Reveles, J Ulises; Saoud, Khaled M; El-Shall, M Samy

2016-10-19

We report a detailed experimental and theoretical study of the gas phase reactivity of Au + with CO, O 2 , N 2 and their mixtures in the presence of a trace amount of water impurity. The gold cation is found to strongly interact with CO and H 2 O molecules via successive addition reactions until reaching saturation. The stoichiometry of the formed complex is determined by the strength of the binding energy of the neutral molecule to the gold cation. CO binds the strongest to Au + , followed by H 2 O, N 2 and then O 2 . We found that the gold cation (Au + ) can activate the O 2 molecule within the Au + (CO) 2 (O 2 ) complex which could react with another CO molecule to form Au + (CO)(CO 2 ) + CO 2 . The product Au + (CO)(CO 2 ) is observed experimentally with a small intensity at room temperature. However, the presence of water leads to the formation of Au + (CO)(H 2 O)(O 2 ) instead of Au + (CO) 2 (O 2 ) due to the strong interaction between Au + and water. The current experiments and calculations might lead to a molecular level understanding of the interactions between the active sites, reactants and impurities which could pave the way for the design of efficient nanocatalysts.

Synthesis of Co2+-doped Fe2O3 photocatalyst for degradation of pararosaniline dye

NASA Astrophysics Data System (ADS)

Suresh, R.; Giribabu, K.; Manigandan, R.; Mangalaraja, R. V.; Solorza, Jorge Yanez; Stephen, A.; Narayanan, V.

2017-06-01

In this paper, x (=2, 5, 7 and 10mol%) Co2+-doped Fe2O3 (xCo:Fe2O3) nanoparticles with enhanced photocatalytic activity have been reported. xCo:Fe2O3 nanoparticles were successfully prepared by co-precipitation followed thermal decomposition method. The structural, optical and morphological properties of the prepared samples were studied by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), diffuse reflectance (DR) UV-visible absorption spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The obtained results revealed that Co2+ ions were well doped within the lattices of Fe2O3. Also, Co2+ ions suppress the formation of the most stable α- Fe2O3 and stabilize less stable γ-Fe2O3 at 450 °C. The photocatalytic activity of xCo:Fe2O3 was examined by using pararosaniline (PR) dye. It was found that photocatalytic degradation of PR depends on dopant concentration (Co2+ ions). Relatively, the highest photocatalytic activity was observed for 5%Co:Fe2O3 nanoparticles. The plausible photocatalytic degradation pathway of PR at xCo:Fe2O3 surface has also been proposed.

Single-coal-particle combustion in O{sub 2}/N{sub 2} and O{sub 2}/CO{sub 2} environments

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

Bejarano, Paula A.; Levendis, Yiannis A.

A fundamental investigation has been conducted on the combustion of single particles of a bituminous coal (45-53, 75-90, and 150-180 {mu}m), of a lignite coal (45-53 and 75-90 {mu}m), and of spherical and monodisperse synthetic chars (43 {mu}m) at increasing O{sub 2} mole fractions in either N{sub 2} or CO{sub 2} balance gases. The synthetic particles were used to facilitate the observation of combustion phenomena with minimum distractions from particle-to-particle variabilities. The laboratory setup consisted of a drop-tube furnace operated at temperatures of 1400 and 1600 K. A calibrated three-color pyrometer, interfaced with the furnace, recorded luminous particle temperature-time profiles.more » Experimental results revealed that coal particles burned at higher mean temperatures and shorter combustion times in O{sub 2}/N{sub 2} than in O{sub 2}/CO{sub 2} environments at analogous oxygen mole fractions. In the case of the bituminous coal used herein and for the experimental combustion conditions tested, measured volatile and char temperatures as in air (21% O{sub 2}) were attained with an oxygen content in the CO{sub 2} mixtures in the neighborhood of 30%. Bituminous coal volatile and char burnout times comparable to those in air (21% O{sub 2}) were attained with oxygen content in the CO{sub 2} mixtures in the range of 30-35%. In the case of the lignite coal burned, the corresponding differences in oxygen mole fractions, which result in similar particle temperatures and burnout times in the two different gas mixtures, were less pronounced. (author)« less

Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

PubMed

Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

2014-02-28

The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

Single-component and binary CO2 and H2O adsorption of amine-functionalized cellulose.

PubMed

Gebald, Christoph; Wurzbacher, Jan A; Borgschulte, Andreas; Zimmermann, Tanja; Steinfeld, Aldo

2014-02-18

A fundamental analysis of single-component and binary CO2 and H2O adsorption of amine-functionalized nanofibrillated cellulose is carried out in the temperature range of 283-353 K and at CO2 partial pressures in the range of 0.02-105 kPa, where the ultralow partial pressure range is relevant for the direct capture of CO2 from atmospheric air. Single-component CO2 and H2O adsorption experimental data are fitted to the Toth and Guggenheim-Anderson-de Boer models, respectively. Corresponding heats of adsorption, derived from explicit solutions of the van't Hoff equation, are -50 kJ/mol CO2 and -48.8 kJ/mol H2O. Binary CO2/H2O adsorption measurements for humid air reveal that the presence of H2O at 2.55 kPa enhances CO2 adsorption, while the presence of CO2 at 0.045 kPa does not influence H2O adsorption. The energy demand of the temperature-vacuum-swing adsorption/desorption cycle for delivering pure CO2 from air increases significantly with H2O adsorption and indicates the need to reduce the hygroscopicity of the adsorbent.

Single photon ionization of van der Waals clusters with a soft x-ray laser: (CO2)n and (CO2)n(H2O)m.

PubMed

Heinbuch, S; Dong, F; Rocca, J J; Bernstein, E R

2006-10-21

Pure neutral (CO2)n clusters and mixed (CO2)n(H2O)m clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV. The distribution of pure (CO2)n clusters decreases roughly exponentially with increasing cluster size. During the ionization process, neutral clusters suffer little fragmentation because almost all excess cluster energy above the vertical ionization energy is taken away by the photoelectron and only a small part of the photon energy is deposited into the (CO2)n cluster. Metastable dissociation rate constants of (CO2)n+ are measured in the range of (0.2-1.5) x 10(4) s(-1) for cluster sizes of 5< or =n< or =16. Mixed CO2-H2O clusters are studied under different generation conditions (5% and 20% CO2 partial pressures and high and low expansion pressures). At high CO2 concentration, predominant signals in the mass spectrum are the (CO2)n+ cluster ions. The unprotonated cluster ion series (CO2)nH2O+ and (CO2)n(H2O)2+ are also observed under these conditions. At low CO2 concentration, protonated cluster ions (H2O)nH+ are the dominant signals, and the protonated CO2(H2O)nH+ and unprotonated (H2O)n+ and (CO2)(H2O)n+ cluster ion series are also observed. The mechanisms and dynamics of the formation of these neutral and ionic clusters are discussed.

The Cheshire-cat-like Behavior of 2nu(sub 3) Overtone of Co2 near 2.134 micron: NIR Lab Spectra of Solid CO2 in H2O and CH3OH

NASA Technical Reports Server (NTRS)

Bernstein, Max; Sandford, Scott; Cruikshank, Dale

2005-01-01

Infrared (IR) spectra have demonstrated that solid H2O is very common in the outer Solar System, and solid carbon dioxide (CO2) has been detected on icy satellites, comets, and planetismals throughout the outer Solar System. In such environments, CO2 and H2O must sometimes be mixed at a molecular level, changing their IR absorption features. In fact, the IR spectra of CO2-H2O mixtures are not equivalent to a linear combination of the spectra of the pure materials. Laboratory IR spectra of pure CO2 and H2O have been published but a lack of near-IR spectra of CO2-H2O mixtures has made the interpretation of outer Solar System spectra more difficult. We present near infrared (IR) spectra of CO2 in H2O and in CH3OH compared to that of pure solid CO2 and find significant differences. Peaks not present in either pure H2O or pure CO2 spectra become evident. First, the CO2 (2nu(sub 3)) overtone near 2.134 micron (4685/ cm) that is not seen in pure solid CO2 is prominent in the spectrum of a CO2/H2O = 25 mixture. Second, a 2.74 micron (3650/ cm) dangling OH feature of water (and a potentially related peak at 1.89 micron) appear in the spectra of CO2-H2O ice mixtures, but may not be specific to the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with water. Changes in CO2 peak positions and profiles on warming of a CO2/H2O = 5 mixture are consistent with 'segregation' of the ice into nearly pure separate components. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 ( 2nu(sub 3)) overtone near 2.134 micron (4685/ cm) is not present in pure CO2 but prominent in mixtures it may be a good observational indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. Significant changes in the near IR spectrum of solid CO2 in the presence of H2O and CH3OH means that the abundance of solid CO2 in the

Measurements and modeling of absorption by CO2 + H2O mixtures in the spectral region beyond the CO2 ν3-band head

NASA Astrophysics Data System (ADS)

Tran, H.; Turbet, M.; Chelin, P.; Landsheere, X.

2018-05-01

In this work, we measured the absorption by CO2 + H2O mixtures from 2400 to 2600 cm-1 which corresponds to the spectral region beyond the ν3 band head of CO2. Transmission spectra of CO2 mixed with water vapor were recorded with a high-resolution Fourier-transform spectrometer for various pressure, temperature and concentration conditions. The continuum absorption by CO2 due to the presence of water vapor was determined by subtracting from measured spectra the contribution of local lines of both species, that of the continuum of pure CO2 as well as of the self- and CO2-continua of water vapor induced by the H2O-H2O and H2O-CO2 interactions. The obtained results are in very good agreement with the unique previous measurement (in a narrower spectral range). They confirm that the H2O-continuum of CO2 is significantly larger than that observed for pure CO2. This continuum thus must be taken into account in radiative transfer calculations for media involving CO2+ H2O mixture. An empirical model, using sub-Lorentzian line shapes based on some temperature-dependent correction factors χ is proposed which enables an accurate description of the experimental results.

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

PubMed Central

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

Quenching of CO2(ν2) by O: New Results and Analysis

NASA Astrophysics Data System (ADS)

Dodd, J. A.; Castle, K. J.; Rhinehart, J. M.; Hwang, E. S.

2005-12-01

New results from ongoing laboratory measurements of CO2(ν2) + O vibrational energy transfer (VET) will be presented. The process is a key contributor to both the CO2 15-μm emission intensity and to upper atmospheric cooling in the 75-120 km altitude range. A 266-nm laser pulse photolyzes O3, producing O atoms and initiating a temperature jump, while transient diode laser absorption spectroscopy is used to monitor the CO2(ν2) level population. We report the latest measurement results, including improvements in the experiment that have mitigated vibrational cascading effects, and the development of a powerful global kinetic fitting routine to allow the simultaneous determination of the appropriate rate parameters from a large body of data. Predictions of upper atmospheric density and temperature are sensitive to the input value of the CO2(ν2) + O relaxation rate constant ko(ν2), including its temperature dependence. Aeronomic models imply that increasing CO2 levels from anthropogenic sources will cause the thermosphere to cool and contract over time. The model results are supported by analyses of satellite orbital motion data over the past 40 years, which are consistent with a few percent thermospheric density decrease per decade. This has important implications for spacecraft drag and orbital longevity. It also provides an interesting connection between a molecular-level parameter, the CO2 + O VET efficiency, and the macroscopic effects of atmospheric density and temperature.

The O2-assisted Al/CO2 electrochemical cell: A system for CO2 capture/conversion and electric power generation.

PubMed

Al Sadat, Wajdi I; Archer, Lynden A

2016-07-01

Economical and efficient carbon capture, utilization, and sequestration technologies are a requirement for successful implementation of global action plans to reduce carbon emissions and to mitigate climate change. These technologies are also essential for longer-term use of fossil fuels while reducing the associated carbon footprint. We demonstrate an O2-assisted Al/CO2 electrochemical cell as a new approach to sequester CO2 emissions and, at the same time, to generate substantial amounts of electrical energy. We report on the fundamental principles that guide operations of these cells using multiple intrusive electrochemical and physical analytical methods, including chronopotentiometry, cyclic voltammetry, direct analysis in real-time mass spectrometry, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, and coupled thermogravimetric analysis-Fourier transform infrared spectroscopy. On this basis, we demonstrate that an electrochemical cell that uses metallic aluminum as anode and a carbon dioxide/oxygen gas mixture as the active material in the cathode provides a path toward electrochemical generation of a valuable (C2) species and electrical energy. Specifically, we show that the cell first reduces O2 at the cathode to form superoxide intermediates. Chemical reaction of the superoxide with CO2 sequesters the CO2 in the form of aluminum oxalate, Al2(C2O4)3, as the dominant product. On the basis of an analysis of the overall CO2 footprint, which considers emissions associated with the production of the aluminum anode and the CO2 captured/abated by the Al/CO2-O2 electrochemical cell, we conclude that the proposed process offers an important strategy for net reduction of CO2 emissions.

The O2-assisted Al/CO2 electrochemical cell: A system for CO2 capture/conversion and electric power generation

PubMed Central

Al Sadat, Wajdi I.; Archer, Lynden A.

2016-01-01

Economical and efficient carbon capture, utilization, and sequestration technologies are a requirement for successful implementation of global action plans to reduce carbon emissions and to mitigate climate change. These technologies are also essential for longer-term use of fossil fuels while reducing the associated carbon footprint. We demonstrate an O2-assisted Al/CO2 electrochemical cell as a new approach to sequester CO2 emissions and, at the same time, to generate substantial amounts of electrical energy. We report on the fundamental principles that guide operations of these cells using multiple intrusive electrochemical and physical analytical methods, including chronopotentiometry, cyclic voltammetry, direct analysis in real-time mass spectrometry, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, and coupled thermogravimetric analysis–Fourier transform infrared spectroscopy. On this basis, we demonstrate that an electrochemical cell that uses metallic aluminum as anode and a carbon dioxide/oxygen gas mixture as the active material in the cathode provides a path toward electrochemical generation of a valuable (C2) species and electrical energy. Specifically, we show that the cell first reduces O2 at the cathode to form superoxide intermediates. Chemical reaction of the superoxide with CO2 sequesters the CO2 in the form of aluminum oxalate, Al2(C2O4)3, as the dominant product. On the basis of an analysis of the overall CO2 footprint, which considers emissions associated with the production of the aluminum anode and the CO2 captured/abated by the Al/CO2-O2 electrochemical cell, we conclude that the proposed process offers an important strategy for net reduction of CO2 emissions. PMID:27453949

CO 2 Adsorption on Anatase TiO 2 (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO 2 Photoreduction

DOE PAGES

Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; ...

2014-10-20

We show how CO 2 adsorption on perfect and reduced anatase TiO 2 (101) surfaces can be substantially modified by the presence of surface Ag and Pt octamer clusters, using density functional theory calculations. Furthermore, we found that adsorption was affected even at sites where the adsorbate was not in direct contact with the octamer, which we attributed to charge donation to CO 2 from the Ag/Pt-modified surface, as well as an electrostatic competition between attractive (Ti–O) and repulsive (Ti–C) interactions. Additionally, TiO 2-supported Pt octamers offer key advantages that could be leveraged for CO 2 photoreduction, including providing additionalmore » stable adsorption sites for bent CO 2 species and facilitating charge transfer to aid in CO 2– anion formation. Electronic structure analysis suggests these factors arise primarily from the hybridization of the bonding molecular orbitals of CO 2 with d orbitals of the Pt atoms. Our results show that, for adsorption on TiO 2-supported Pt octamers, the O–C–O bending and C–O asymmetric stretching frequencies can be used as reliable indicators of the presence of the CO 2– anion intermediate as well as to distinguish unique adsorption geometries or sites. Finally, we suggest a possible pathway for subsequent CO 2 dissociation to CO at the surface of a reduced anatase TiO 2 (101)-supported Pt octamer, which has a computed energy barrier of 1.01 eV.« less

Measuring CO 2 and N 2 O Mass Transfer into GAP-1 CO 2 –Capture Solvents at Varied Water Loadings

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

Whyatt, Greg A.; Zwoster, Andy; Zheng, Feng

This paper investigates the CO 2 and N 2 O absorption behavior in the water-lean gamma amino propyl (GAP)-1/TEG solvent system using a wetted-wall contactor. Testing was performed on a blend of GAP-1 aminosilicone in triethylene glycol at varied water loadings in the solvent. Measurements were made with CO 2 and N 2 O at representative lean (0.04 mol CO 2/mol alkalinity), middle (0.13 mol CO 2 /mol alkalinity) and rich (0.46 mol CO 2 /mol alkalinity) solvent loadings at 0, 5, 10 and 15 wt% water loadings at 40, 60 and 80C° and N 2 O at (0.08-0.09 molmore » CO 2 /mol alkalinity) at 5 wt% water at 40, 60 and 80C°. CO 2 flux was found to be non-linear with respect to log mean pressure driving force (LMPD). Liquid-film mass transfer coefficients (k'g) were calculated by subtracting the gas film resistance (determined from a correlation from literature) from the overall mass transfer measurement. The resulting k'g values for CO 2 and N 2 O in GAP-1/TEG mixtures were found to be higher than that of 5M aqueous monoethanolamine under comparable driving force albeit at higher solvent viscosities. The k'g values for CO 2 were also found to decrease with increasing solvent water content and increase with a decrease in temperature. These observations indicate that mass transfer of CO 2 in GAP-1/TEG is linked to the physical solubility of CO 2 , which is higher in organic solvents compared to water. This paper expands on the understanding of the unique mass transfer behavior and kinetics of CO 2 capture in water-lean solvents.« less

Fabrication and magnetic properties of Fe and Co co-doped ZrO2

NASA Astrophysics Data System (ADS)

Okabayashi, J.; Kono, S.; Yamada, Y.; Nomura, K.

2011-12-01

We investigate the effects of Fe and Co co-doping on the magnetic and electronic properties of ZrO2 ceramics prepared by a sol-gel method, and study their dependence on the annealing temperature. Dilute Fe and Co co-doping into ZrO2 exhibits ferromagnetic behavior at room temperature for annealing temperatures above 900 °C, accompanying the phase transition from tetragonal to monoclinic structure in ZrO2. The electronic structures are studied by x-ray absorption spectroscopy and Mössbauer spectroscopy, which suggest that the Fe3+ and Co2+/Co3+ mixing states are dominant in Fe and Co co-doped ZrO2.

Mechano-chemical pathways to H2O and CO2 splitting

NASA Astrophysics Data System (ADS)

Vedadi, Mohammad H.; Haas, Stephan

2011-10-01

The shock-induced collapse of CO2-filled nanobubbles is investigated using molecular dynamics simulations based on a reactive force field. The energetic nanojet and high-pressure water hammer shock formed during and after collapse of the nanobubble trigger mechano-chemical H2O-CO2 reactions, some of which lead to splitting of water and formation of O2 molecules. The dominant pathways through which splitting of water molecules occur are identified.

Catalase-dependent H2O2 consumption by cardiac mitochondria and redox-mediated loss in insulin signaling.

PubMed

Rindler, Paul M; Cacciola, Angela; Kinter, Michael; Szweda, Luke I

2016-11-01

We have recently demonstrated that catalase content in mouse cardiac mitochondria is selectively elevated in response to high dietary fat, a nutritional state associated with oxidative stress and loss in insulin signaling. Catalase and various isoforms of glutathione peroxidase and peroxiredoxin each catalyze the consumption of H 2 O 2 Catalase, located primarily within peroxisomes and to a lesser extent mitochondria, has a low binding affinity for H 2 O 2 relative to glutathione peroxidase and peroxiredoxin. As such, the contribution of catalase to mitochondrial H 2 O 2 consumption is not well understood. In the current study, using highly purified cardiac mitochondria challenged with micromolar concentrations of H 2 O 2 , we found that catalase contributes significantly to mitochondrial H 2 O 2 consumption. In addition, catalase is solely responsible for removal of H 2 O 2 in nonrespiring or structurally disrupted mitochondria. Finally, in mice fed a high-fat diet, mitochondrial-derived H 2 O 2 is responsible for diminished insulin signaling in the heart as evidenced by reduced insulin-stimulated Akt phosphorylation. While elevated mitochondrial catalase content (∼50%) enhanced the capacity of mitochondria to consume H 2 O 2 in response to high dietary fat, the selective increase in catalase did not prevent H 2 O 2 -induced loss in cardiac insulin signaling. Taken together, our results indicate that mitochondrial catalase likely functions to preclude the formation of high levels of H 2 O 2 without perturbing redox-dependent signaling. Copyright © 2016 the American Physiological Society.

Chemical weathering rate, denudation rate, and atmospheric and soil CO2 consumption of Paraná flood basalts in São Paulo State, Brazil

NASA Astrophysics Data System (ADS)

da Conceição, Fabiano Tomazini; dos Santos, Carolina Mathias; de Souza Sardinha, Diego; Navarro, Guillermo Rafael Beltran; Godoy, Letícia Hirata

2015-03-01

The chemical weathering rate and atmospheric/soil CO2 consumption of Paraná flood basalts in the Preto Stream basin, São Paulo State, Brazil, were evaluated using major elements as natural tracers. Surface and rain water samples were collected in 2006, and analyses were performed to assess pH, temperature, dissolved oxygen (DO), electrical conductivity (EC) and total dissolved solids (TDS), including SO42-, NO3-, PO43 -, HCO3-, Cl-, SiO2, Ca2 +, Mg2 +, Na+ and K+. Fresh rocks and C horizon samples were also collected, taking into account their geological context, abundance and spatial distribution, to analyze major elements and mineralogy. The Preto Stream, downstream from the city of Ribeirão Preto, receives several elements/compounds as a result of anthropogenic activities, with only sulfate yielding negative flux values. The negative flux of SO42 - can be attributed to atmospheric loading that is mainly related to anthropogenic inputs. After corrections were made for atmospheric inputs, the riverine transport of dissolved material was found to be 30 t km- 2 y- 1, with the majority of the dissolved material transported during the summer (wet) months. The chemical weathering rate and atmospheric/soil CO2 consumption were 6 m/Ma and 0.4 · 106 mol km- 2 y- 1, respectively. The chemical weathering rate falls within the lower range of Paraná flood basalt denudation rates between 135 and 35 Ma previously inferred from chronological studies. This comparison suggests that rates of basalt weathering in Brazil's present-day tropical climate differ by at most one order of magnitude from those prevalent at the time of hothouse Earth. The main weathering process is the monosiallitization of anorthoclase, augite, anorthite and microcline. Magnetite is not weathered and thus remains in the soil profile.

UiO-66-NH2/GO Composite: Synthesis, Characterization and CO2 Adsorption Performance

PubMed Central

Cao, Yan; Zhang, Hongmei; Song, Fujiao; Huang, Tao; Ji, Jiayu; Zhong, Qin; Chu, Wei; Xu, Qi

2018-01-01

In this work, a new composite materials of graphene oxide (GO)-incorporated metal-organic framework (MOF)(UiO-66-NH2/GO) were in-situ synthesized, and were found to exhibit enhanced high performances for CO2 capture. X-ray diffraction (XRD), scanning electron microscope (SEM), N2 physical adsorption, and thermogravimetric analysis (TGA) were applied to investigate the crystalline structure, pore structure, thermal stability, and the exterior morphology of the composite. We aimed to investigate the influence of the introduction of GO on the stability of the crystal skeleton and pore structure. Water, acid, and alkali resistances were tested for physical and chemical properties of the new composites. CO2 adsorption isotherms of UiO-66, UiO-66-NH2, UiO-66/GO, and UiO-66-NH2/GO were measured at 273 K, 298 K, and 318 K. The composite UiO-66-NH2/GO exhibited better optimized CO2 uptake of 6.41 mmol/g at 273 K, which was 5.1% higher than that of UiO-66/GO (6.10 mmol/g). CO2 adsorption heat and CO2/N2 selectivity were then calculated to further evaluate the CO2 adsorption performance. The results indicated that UiO-66-NH2/GO composites have a potential application in CO2 capture technologies to alleviate the increase in temperature of the earth’s atmosphere. PMID:29641476

CO2 in solid para-hydrogen: spectral splitting and the CO2···(o-H2)n clusters.

PubMed

Du, Jun-He; Wan, Lei; Wu, Lei; Xu, Gang; Deng, Wen-Ping; Liu, An-Wen; Chen, Yang; Hu, Shui-Ming

2011-02-17

Complicated high-resolution spectral structures are often observed for molecules doped in solid molecular hydrogen. The structures can result from miscellaneous effects and are often interpreted differently in references. The spectrum of the ν(3) band of CO(2) in solid para-H(2) presents a model system which exhibits rich spectral structures. With the help of the potential energy simulation of the CO(2) molecule doped in para-hydrogen matrix, and extensive experiments with different CO(2) isotopologues and different ortho-hydrogen concentrations in the matrix, the spectral features observed in p-H(2) matrix are assigned to the CO(2)···(o-H(2))(n) clusters and also to energy level splitting that is due to different alignments of the doped CO(2) molecules in the matrix. The assignments are further supported by the dynamics analysis and also by the spectrum recorded with sample codoped with O(2) which serves as catalyst transferring o-H(2) to p-H(2) in the matrix at 4 K temperature. The observed spectral features of CO(2)/pH(2) can potentially be used as an alternative readout of the temperature and orthohydrogen concentration in the solid para-hydrogen.

Oxidation of alloys for energy applications in supercritical CO 2 and H 2O

DOE PAGES

Holcomb, Gordon R.; Carney, Casey; Doğan, Ömer N.

2016-03-19

To facilitate development of supercritical CO 2 (sCO 2) power plants, a comparison of the oxidation behavior of austenitic stainless steels and Ni-base alloys in sH 2O and sCO 2 were made. Experiments were conducted at 730 °C/207 bar (sCO 2) and 726 °C/208 bar (sH 2O). Ni-base alloys in sCO 2 did not exhibit much change with pressure. Ni-base alloys in sH 2O had an increase in corrosion rate and the log of the parabolic rate constant was proportional to pressure. Lastly, fine-grain austenitic stainless steels in sCO 2 and sH 2O were both less protective with pressure asmore » the dense protective chromia scale was replaced with faster growing Fe-oxide rich scales.« less

Investigations on the Synthesis and Properties of Fe2O3/Bi2O2CO3 in the Photocatalytic and Fenton-like Process

NASA Astrophysics Data System (ADS)

Sun, Dongxue; Shen, Tingting; Sun, Jing; Wang, Chen; Wang, Xikui

2018-01-01

Catalyst of Bi2O2CO3 and Fe2O3 modified Bi2O2CO3 (Fe2O3/Bi2O2CO3) were prepared by hydrothermal method and characterized by X-ray diffractions (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and UV-vis DRS. The catalytic activity of Bi2O2CO3 and Fe2O3/Bi2O2CO3 were comparatively investigated in the photodegradation and Fento-like process. Rhodamine B(RhB) was selected as the target pollutant under the irradiation of 300 W xenon lamp. The results indicated that Fe2O3 plays a great role in the enhancing the treatment efficiency and the and the maximum reaction rate was achieved at the Fe2O3 loading of 1.5%. The Fenton-like degradation rate constant of RhB with bare Bi2O2CO3 in dark is 0.4 min-1, while that with 1.5 Fe2O3/Bi2O2CO3 increases to 28.4 min-1 under visible light irradiation, a 71-fold improvement. It is expected to shed a new light for the constructing novel composite photocatalyst and also provide a potential method for the removal of dyes in the aqueous system.

Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

PubMed

Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

2015-01-07

Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

A kinetic study of Ca-containing ions reacting with O, O2, CO2 and H2O: implications for calcium ion chemistry in the upper atmosphere.

PubMed

Broadley, Sarah; Vondrak, Tomas; Wright, Timothy G; Plane, John M C

2008-09-14

A series of gas-phase reactions involving molecular Ca-containing ions was studied by the pulsed laser ablation of a calcite target to produce Ca+ in a fast flow of He, followed by the addition of reagents downstream and detection of ions by quadrupole mass spectrometry. Most of the reactions that were studied are important for describing the chemistry of meteor-ablated calcium in the earth's upper atmosphere. The following rate coefficients were measured: k(CaO+ + O --> Ca+ + O2) = (4.2 +/- 2.8) x 10(-11) at 197 K and (6.3 +/- 3.0) x 10(-11) at 294 K; k(CaO+ + CO --> Ca+ + CO2, 294 K) = (2.8 +/- 1.5) x 10(-10); k(Ca+.CO2 + O2 --> CaO2+ + CO2, 294 K) = (1.2 +/- 0.5) x10(-10); k(Ca+.CO2 + H2O --> Ca+.H2O + CO2) = (13.0 +/- 4.0) x 10(-10); and k(Ca+.H2O + O2 --> CaO2+ + H2O, 294 K) = (4.0 +/- 2.5) x 10(-10) cm3 molecule(-1) s(-1). The quoted uncertainties are a combination of the 1 sigma standard errors in the kinetic data and the systematic errors in the models used to extract the rate coefficients. Rate coefficients were also obtained for the following recombination (also termed association) reactions in He bath gas: k(Ca+.CO2 + CO2 --> Ca+.(CO2)2, 294 K) = (2.6 +/- 1.0) x 10(-29); k(Ca+.H2O + H2O --> Ca+.(H2O)2) = (1.6 +/- 1.1) x 10(-27); and k(CaO2+ + O2 --> CaO2+.O2) < 1 x 10(-31) cm6 molecule(-2) s(-1). These recombination rate coefficients, as well as those for the ligand-switching reactions listed above, were then interpreted using a combination of high level quantum chemistry calculations and RRKM theory using an inverse Laplace transform solution of the master equation. The surprisingly slow reaction between CaO+ and O was explained using quantum chemistry calculations on the lowest 2A', 2A'' and 4A'' potential energy surfaces. These calculations indicate that reaction mostly occurs on the 2A' surface, leading to production of Ca+ (2S) + O2(1 Delta g). The importance of this reaction for controlling the lifetime of Ca+ in the upper mesosphere and lower

Intrinsically modified thermoelectric performance of alkaline-earth isovalently substituted [Bi2AE2O4][CoO2]y single crystals

NASA Astrophysics Data System (ADS)

Sun, N.; Dong, S. T.; Zhang, B. B.; Chen, Y. B.; Zhou, J.; Zhang, S. T.; Gu, Z. B.; Yao, S. H.; Chen, Y. F.

2013-07-01

Alkaline-earth elements isovalently substituted into a [Bi2AE2O4][CoO2]y (AE2 = Ca2, Sr2, and CaSr) single crystal with a layered structure were grown by the optical floating zone method. Structural characterization by X-ray diffraction and electron microscopy showed that the layers were oriented perpendicular to the c-axis, as well as the growth of direction was parallel to the ab-plane. The thermoelectric properties, including the Seebeck effect, electrical conductivity and thermal conductivity were investigated. The results of the thermoelectric measurements showed that the full substitution of Ca for Sr in [Bi2Sr2-xCaxO4][CoO2]y has the best overall thermoelectric performance. Compared with the other two cases studied, the full Ca substituted crystal [Bi2Ca2O4][CoO2]y exhibits both reduced resistivity and thermal conductivity, but not a reduced Seebeck coefficient. The enhanced thermoelectric property in [Bi2Ca2O4][CoO2]y is mainly due to lower structural symmetry, which is confirmed by electron microscopy characterization. This work demonstrates that even isovalently substitution can play a crucial role in the thermoelectric effect of layered cobalt oxides.

Modification of Ga2O3 by an Ag-Cr core-shell cocatalyst enhances photocatalytic CO evolution for the conversion of CO2 by H2O.

PubMed

Pang, Rui; Teramura, Kentaro; Tatsumi, Hiroyuki; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2018-01-25

A core-shell structure of Ag-Cr dual cocatalyst loaded-Ga 2 O 3 was found to significantly enhance the formation rate of CO and selectivity toward CO evolution for the photocatalytic conversion of CO 2 where H 2 O is used as an electron donor.

Role of SiO2 coating in multiferroic CoCr2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Kamran, M.; Ullah, Asmat; Mehmood, Y.; Nadeem, K.; Krenn, H.

2017-02-01

Effect of silica (SiO2) coating concentration on structural and magnetic properties of multiferroic cobalt chromite (CoCr2O4) nanoparticles have been studied. The nanoparticles with average crystallite size in the range 19 to 28 nm were synthesised by sol-gel method. X-ray diffraction (XRD) analysis has verified the composition of single-phase cubic normal spinel structure of CoCr2O4 nanoparticles. The average crystallite size and cell parameter decreased with increasing SiO2 concentration. TEM image revealed that the shape of nanoparticles was non-spherical. Zero field cooled/field cooled (ZFC/FC) curves revealed that nanoparticles underwent a transition from paramagnetic (PM) state to collinear short-range ferrimagnetic (FiM) state, and this PM-FiM transition temperature decreased from 101 to 95 K with increasing SiO2 concentration or decreasing crystallite size. A conical spin state at Ts = 27 K was also observed for all the samples which decreased with decreasing average crystallite size. Low temperature lock-in transition was also observed in these nanoparticles at 12 K for uncoated nanoparticles which slightly shifted towards low temperature with decreasing average crystallite size. Saturation magnetization (Ms) showed decreasing trend with increasing SiO2 concentration, which was due to decrease in average crystallite size of nanoparticles and enhanced surface disorder in smaller nanoparticles. The temperature dependent AC-susceptibility also showed the decrease in the transition temperature (Tc), broadening of the Tc peak and decrease in magnetization with increasing SiO2 concentration or decreasing average crystallite size. In summary, the concentration of SiO2 has significantly affected the structural and magnetic properties of CoCr2O4 nanoparticles.

Modulated exchange bias in NiFe/CoO/α-Fe2O3 trilayers and NiFe/CoO bilayers

NASA Astrophysics Data System (ADS)

Li, X.; Lin, K.-W.; Yeh, W.-C.; Desautels, R. D.; van Lierop, J.; Pong, Philip W. T.

2017-02-01

While the exchange bias in ferromagnetic/antiferromagnetic (FM/AF) bilayer and FM1/AF/FM2 trilayer configurations has been widely investigated, the role of an AF2 layer in FM/AF1/AF2 trilayer configurations is still not well understood. In this work, the magnetic properties of NiFe/CoO, NiFe/α-Fe2O3 bilayers, and NiFe/CoO/α-Fe2O3 trilayer were studied comparatively. The microstructure and chemical composition were characterized. Temperature dependent magnetometry reveals increased irreversibility temperature in NiFe/CoO/α-Fe2O3 trilayer compared with NiFe/CoO bilayer. The magnetic hysteresis loops show that the exchange bias (Hex) and coercivity (Hc) depend strongly on the anisotropy of AF layer (CoO, α-Fe2O3 and CoO/α-Fe2O3). Our work shows that the AF1/AF2 interfacial interactions can be used effectively for tuning the exchange bias in FM/AF1/AF2 trilayers.

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.

Outsourcing CO2 Emissions

NASA Astrophysics Data System (ADS)

Davis, S. J.; Caldeira, K. G.

2009-12-01

CO2 emissions from the burning of fossil fuels are the primary cause of global warming. Much attention has been focused on the CO2 directly emitted by each country, but relatively little attention has been paid to the amount of emissions associated with consumption of goods and services in each country. This consumption-based emissions inventory differs from the production-based inventory because of imports and exports of goods and services that, either directly or indirectly, involved CO2 emissions. Using the latest available data and reasonable assumptions regarding trans-shipment of embodied carbon through third-party countries, we developed a global consumption-based CO2 emissions inventory and have calculated associated consumption-based energy and carbon intensities. We find that, in 2004, 24% of CO2 emissions are effectively outsourced to other countries, with much of the developed world outsourcing CO2 emissions to emerging markets, principally China. Some wealthy countries, including Switzerland and Sweden, outsource over half of their consumption-based emissions, with many northern Europeans outsourcing more than three tons of emissions per person per year. The United States is both a big importer and exporter of emissions embodied in trade, outsourcing >2.6 tons of CO2 per person and at the same time as >2.0 tons of CO2 per person are outsourced to the United States. These large flows indicate that CO2 emissions embodied in trade must be taken into consideration when considering responsibility for increasing atmospheric greenhouse gas concentrations.

One-step facile hydrothermal synthesis of Fe2O3@LiCoO2 composite as excellent supercapacitor electrode materials

NASA Astrophysics Data System (ADS)

Gopi, Chandu V. V. Muralee; Somasekha, A.; Reddy, Araveeti Eswar; Kim, Soo-Kyoung; Kim, Hee-Je

2018-03-01

Herein, for the first time, we demonstrate the fabrication of Fe2O3@LiCoO2 hybrid nanostructures on Ni foam substrate by facile one-step hydrothermal technique. Morphological studies reveal that aggregated Fe2O3 nanoflakes anchored on the surface of sphere-like LiCoO2 nanoflakes. Electrochemical studies are used to examine the performance of the supercapacitor electrodes. The composite Fe2O3@LiCoO2 electrode exhibited excellent electrochemical performance than Fe2O3 and LiCoO2 electrodes, such as a low charge transfer resistance, a high specific capacitance of 489 F g-1 at 5 mA cm-2 and an enhanced capacity retention of 108% over 3000 cycles at 15 mA cm-2. The composite Fe2O3@LiCoO2 holds great promise for electrochemical applications due to well-defined hierarchical morphology, synergetic effect of Fe2O3 and LiCoO2, enhanced electrical conductivity, efficient electrolyte penetration and fast electron transfer.

China's growing CO2 emissions--a race between increasing consumption and efficiency gains.

PubMed

Peters, Glen P; Weber, Christopher L; Guan, Dabo; Hubacek, Klaus

2007-09-01

China's rapidly growing economy and energy consumption are creating serious environmental problems on both local and global scales. Understanding the key drivers behind China's growing energy consumption and the associated CO2 emissions is critical for the development of global climate policies and provides insight into how other emerging economies may develop a low emissions future. Using recently released Chinese economic input-output data and structural decomposition analysis we analyze how changes in China's technology, economic structure, urbanization, and lifestyles affect CO2 emissions. We find that infrastructure construction and urban household consumption, both in turn driven by urbanization and lifestyle changes, have outpaced efficiency improvements in the growth of CO2 emissions. Net trade had a small effect on total emissions due to equal, but significant, growth in emissions from the production of exports and emissions avoided by imports. Technology and efficiency improvements have only partially offset consumption growth, but there remains considerable untapped potential to reduce emissions by improving both production and consumption systems. As China continues to rapidly develop there is an opportunity to further implement and extend policies, such as the Circular Economy, that will help China avoid the high emissions path taken by today's developed countries.

Extraction of Mg(OH)2 from Mg silicate minerals with NaOH assisted with H2O: implications for CO2 capture from exhaust flue gas.

PubMed

Madeddu, Silvia; Priestnall, Michael; Godoy, Erik; Kumar, R Vasant; Raymahasay, Sugat; Evans, Michael; Wang, Ruofan; Manenye, Seabelo; Kinoshita, Hajime

2015-01-01

The utilisation of Mg(OH)2 to capture exhaust CO2 has been hindered by the limited availability of brucite, the Mg(OH)2 mineral in natural deposits. Our previous study demonstrated that Mg(OH)2 can be obtained from dunite, an ultramafic rock composed of Mg silicate minerals, in highly concentrated NaOH aqueous systems. However, the large quantity of NaOH consumed was considered an obstacle for the implementation of the technology. In the present study, Mg(OH)2 was extracted from dunite reacted in solid systems with NaOH assisted with H2O. The consumption of NaOH was reduced by 97% with respect to the NaOH aqueous systems, maintaining a comparable yield of Mg(OH)2 extraction, i.e. 64.8-66%. The capture of CO2 from a CO2-N2 gas mixture was tested at ambient conditions using a Mg(OH)2 aqueous slurry. Mg(OH)2 almost fully dissolved and reacted with dissolved CO2 by forming Mg(HCO3)2 which remained in equilibrium storing the CO2 in the aqueous solution. The CO2 balance of the process was assessed from the emissions derived from the power consumption for NaOH production and Mg(OH)2 extraction together with the CO2 captured by Mg(OH)2 derived from dunite. The process resulted as carbon neutral when dunite is reacted at 250 °C for durations of 1 and 3 hours and CO2 is captured as Mg(HCO3)2.

Economic growth, energy consumption and CO2 emissions in India: a disaggregated causal analysis

NASA Astrophysics Data System (ADS)

Nain, Md Zulquar; Ahmad, Wasim; Kamaiah, Bandi

2017-09-01

This study examines the long-run and short-run causal relationships among energy consumption, real gross domestic product (GDP) and CO2 emissions using aggregate and disaggregate (sectoral) energy consumption measures utilising annual data from 1971 to 2011. The autoregressive distributed lag bounds test reveals that there is a long-run relationship among the variables concerned at both aggregate and disaggregate levels. The Toda-Yamamoto causality tests, however, reveal that the long-run as well short-run causal relationship among the variables is not uniform across sectors. The weight of evidences of the study indicates that there is short-run causality from electricity consumption to economic growth, and to CO2 emissions. The results suggest that India should take appropriate cautious steps to sustain high growth rate and at the same time to control emissions of CO2. Further, energy and environmental policies should acknowledge the sectoral differences in the relationship between energy consumption and real gross domestic product.

Kinetic and stoichiometric constraints determine the pathway of H2O2 consumption by red blood cells.

PubMed

Orrico, Florencia; Möller, Matías N; Cassina, Adriana; Denicola, Ana; Thomson, Leonor

2018-05-09

Red blood cells (RBC) are considered as a circulating sink of H 2 O 2 , but a significant debate remains over the role of the different intraerythocyte peroxidases. Herein we examined the kinetic of decomposition of exogenous H 2 O 2 by human RBC at different cell densities, using fluorescent and oxymetric methods, contrasting the results against a mathematical model. Fluorescent measurements as well as oxygen production experiments showed that catalase was responsible for most of the decomposition of H 2 O 2 at cell densities suitable for both experimental settings (0.1-10 × 10 10 cell L -1 ), since sodium azide but not N-ethylmaleimide (NEM) inhibited H 2 O 2 consumption. Oxygen production decreased at high cell densities until none was detected above 1.1 × 10 12 cell L- 1 , being recovered after inhibition of the thiol dependent systems by NEM. This result underlined that the consumption of H 2 O 2 by catalase prevail at RBC densities regularly used for research, while the thiol dependent systems predominate when the cell density increases, approaching the normal number in blood (5 × 10 12 cell L- 1 ). The mathematical model successfully reproduced experimental results and at low cell number it showed a time sequence involving Prx as the first line of defense, followed by catalase, with a minor role by Gpx. The turning points were given by the total consumption of reduced Prx in first place and reduced GSH after that. However, Prx alone was able to account for the added H 2 O 2 (50µM) at physiological RBC density, calling attention to the importance of cell density in defining the pathway of H 2 O 2 consumption and offering an explanation to current apparently conflicting results in the literature. Copyright © 2018. Published by Elsevier Inc.

Enhanced photocatalytic CO2 reduction to CH4 over separated dual co-catalysts Au and RuO2

NASA Astrophysics Data System (ADS)

Dong, Chunyang; Hu, Songchang; Xing, Mingyang; Zhang, Jinlong

2018-04-01

A spatially separated, dual co-catalyst photocatalytic system was constructed by the stepwise introduction of RuO2 and Au nanoparticles (NPs) at the internal and external surfaces of a three dimensional, hierarchically ordered TiO2-SiO2 (HTSO) framework (the final photocatalyst was denoted as Au/HRTSO). Characterization by HR-TEM, EDS-mapping, XRD and XPS confirmed the existence and spatially separated locations of Au and RuO2. In CO2 photocatalytic reduction (CO2PR), Au/HRTSO (0.8%) shows the optimal performance in both the activity and selectivity towards CH4; the CH4 yield is almost twice that of the singular Au/HTSO or HRTSO (0.8%, weight percentage of RuO2) counterparts. Generally, Au NPs at the external surface act as electron trapping agents and RuO2 NPs at the inner surface act as hole collectors. This advanced spatial configuration could promote charge separation and transfer efficiency, leading to enhanced CO2PR performance in both the yield and selectivity toward CH4 under simulated solar light irradiation.

Polytherm of the CO(NH2)2-KNO3-H2O phase diagram

NASA Astrophysics Data System (ADS)

Yulina, I. V.; Trunin, A. S.

2017-05-01

The crystallization polytherm of the ternary CO(NH2)2-KNO3-H2O system is plotted for the first time via visual polythermal analysis and calculating ternary eutonics characteristics from data on the boundary elements of two-component systems. The ternary eutonics modeling error does not exceed 3.5%. In addition to the crystallization fields of individual components, the field of the redox reaction that occurs in the system between potassium nitrate and carbamide is shown in the CO(NH2)2-KNO3-H2O diagram by a dashed outline.

Porous MnCo2O4 as superior anode material over MnCo2O4 nanoparticles for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Baji, Dona Susan; Jadhav, Harsharaj S.; Nair, Shantikumar V.; Rai, Alok Kumar

2018-06-01

Pyro synthesis is a method to coat nanoparticles by uniform layer of carbon without using any conventional carbon source. The resultant carbon coating can be evaporated in the form of CO or CO2 at high temperature with the creation of large number of nanopores on the sample surface. Hence, a porous MnCo2O4 is successfully synthesized here with the same above strategy. It is believed that the electrolyte can easily permeate through these nanopores into the bulk of the sample and allow rapid access of Li+ ions during charge/discharge cycling. In order to compare the superiority of the porous sample synthesized by pyro synthesis method, MnCo2O4 nanoparticles are also synthesized by sol-gel synthesis method at the same parameters. When tested as anode materials for lithium ion battery application, porous MnCo2O4 electrode shows high capacity with long lifespan at all the investigated current rates in comparison to MnCo2O4 nanoparticles electrode.

Energy consumption and CO2 emissions in Tibet and its cities in 2014

NASA Astrophysics Data System (ADS)

Shan, Yuli; Zheng, Heran; Guan, Dabo; Li, Chongmao; Mi, Zhifu; Meng, Jing; Schroeder, Heike; Ma, Jibo; Ma, Zhuguo

2017-08-01

Because of its low level of energy consumption and the small scale of its industrial development, the Tibet Autonomous Region has historically been excluded from China's reported energy statistics, including those regarding CO2 emissions. In this paper, we estimate Tibet's energy consumption using limited online documents, and we calculate the 2014 energy-related and process-related CO2 emissions of Tibet and its seven prefecture-level administrative divisions for the first time. Our results show that 5.52 million tons of CO2 were emitted in Tibet in 2014; 33% of these emissions are associated with cement production. Tibet's emissions per capita amounted to 1.74 tons in 2014, which is substantially lower than the national average, although Tibet's emission intensity is relatively high at 0.60 tons per thousand yuan in 2014. Among Tibet's seven prefecture-level administrative divisions, Lhasa City and Shannan Region are the two largest CO2 contributors and have the highest per capita emissions and emission intensities. The Nagqu and Nyingchi regions emit little CO2 due to their farming/pasturing-dominated economies. This quantitative measure of Tibet's regional CO2 emissions provides solid data support for Tibet's actions on climate change and emission reductions.

Dissecting the steps of CO2 reduction: 1. The interaction of CO and CO2 with γ-Al2O3: an in situ FTIR study

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

Szanyi, Janos; Kwak, Ja Hun

2014-08-07

The adsorption of CO2 and CO was investigated on a pure γ-Al2O3 support material that has been used for the preparation of Pd and Ru catalysts for the catalytic reduction of CO2. The adsorption of CO2 resulted in the formation of carbonates, bicarbonates and linearly adsorbed CO2 species. The amount and the nature of the adsorbed species were dependent on the annealing temperature of the alumina support. On γ-Al2O3 annealed at 473 K mostly bicarbonates formed, while no adsorbed CO2 was seen on this highly hydroxylated surface. With increasing calcinations temperature, i.e., increasing extent of dehydroxylation, the amounts of bothmore » surface nitrates and linear adsorbed CO2 increased, but still the most abundant surface species were bicarbonates. Surface carbonates and adsorbed CO2 can readily be removed from the alumina surface, while bicarbonates are stable to elevated temperatures. The interaction of CO with γ-Al2O3 is much weaker than that of CO2. At room temperatures CO adsorbs only on Lewis acid sites, and can be readily removed by evacuation. At 100 K CO can probe different defect sites on the alumina surface (both Lewis acid sites and surface hydroxyls). Under no conditions we have observed the formation of any carbonates or bicarbonates upon the interaction of CO with the pure alumina support. In co-adsorption experiments CO competes for adsorption sites with the linearly adsorbed CO2 on the 773 K-annealed γ-Al2O3 surface; but it does not result in the desorption of CO2, rather in the increase of weakly-held carbonate production. After the removal of adsorbed CO, CO2 moves back to its original adsorption sites, i.e., Lewis acidic Al3+ centers. The exposure of a CO2-saturated γ-Al2O3 to H2O did not affect any of the adsorbed surface species. The findings of this study will be used to rationalize the results of our ongoing in situ and in operando studies on the reduction of CO2 on supported Pd and Ru catalysts. Acknowledgements: We gratefully

CO2 leakage-induced vegetation decline is primarily driven by decreased soil O2.

PubMed

Zhang, Xueyan; Ma, Xin; Zhao, Zhi; Wu, Yang; Li, Yue

2016-04-15

To assess the potential risks of carbon capture and storage (CCS), studies have focused on vegetation decline caused by leaking CO2. Excess soil CO2 caused by leakage can affect soil O2 concentrations and soil pH, but how these two factors affect plant development remains poorly understood. This hinders the selection of appropriate species to mitigate potential negative consequences of CCS. Through pot experiments, we simulated CO2 leakage to examine its effects on soil pH and soil O2 concentrations. We subsequently assessed how maize growth responded to these changes in soil pH and O2. Decreased soil O2 concentrations significantly reduced maize biomass, and explained 69% of the biomass variation under CO2 leakage conditions. In contrast, although leaked CO2 changed soil pH significantly (from 7.32 to 6.75), it remained within the optimum soil pH range for maize growth. This suggests that soil O2 concentration, not soil pH, influences plant growth in these conditions. Therefore, in case of potential CO2 leakage risks, hypoxia-tolerant species should be chosen to improve plant survival, growth, and yield. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of Fe3O4/SiO2/Gd2O(CO3)2 core/shell/shell nanoparticles as T1 and T2 dual mode MRI contrast agent.

PubMed

Yang, Meicheng; Gao, Lipeng; Liu, Kai; Luo, Chunhua; Wang, Yiting; Yu, Lei; Peng, Hui; Zhang, Wen

2015-01-01

Core/shell/shell structured Fe3O4/SiO2/Gd2O(CO3)2 nanoparticles were successfully synthesized. Their properties as a new type of T1-T2 dual model contrast agent for magnetic resonance imaging were investigated. Due to the introduce of a separating SiO2 layer, the magnetic coupling between Gd2O(CO3)2 and Fe3O4 could be modulated by the thickness of SiO2 layer and produce appropriate T1 and T2 signal. Additionally, the existence of Gd(3+) enhances the transverse relaxivity of Fe3O4 possibly because of the magnetic coupling between Gd(3+) and Fe3O4. The Fe3O4/SiO2/Gd2O(CO3)2 nanoparticles exhibit good biocompatibility, showing great potential for biomedical applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Interdependence of arterial PO2 and O2 consumption in the fetal sheep.

PubMed

Asakura, H; Ball, K T; Power, G G

1990-04-01

These experiments were undertaken to measure the effects of changing arterial oxygen tension (PaO2) on oxygen use by the fetal body (VO2). Six fetal sheep at 130-140 days gestation were prepared with an endotracheal tube, carotid artery catheter, body-core thermistor, cooling coil and loosely-applied umbilical cord snare. The next day the cord was occluded and the fetal lungs were ventilated with gas mixtures containing different concentrations of oxygen. While fetal core temperature was kept constant, fetal arterial PO2 was cycled between high and low values (span = 7 to 359 mmHg, n = 103) and O2 consumption was measured by the rate of O2 uptake from a closed-rebreathing circuit. VO2 changed directly with changes in PO2 from 10 to 40 mmHg but became insensitive to changes in PO2 above about 50 mmHg. The results were well described over the entire range by the equation: VO2 (ml/min per kg fetal wt) = -9.62 + 6.99 ln PO2(mmHg)-0.66 ln2 PO2. Thus the oxygen consumption of the near-term fetal sheep varies with changes in arterial PO2 in the physiologic range. This finding is distinctly different than the adult at rest but resembles adult tissues such as exercising muscle at VO2max. This finding is consistent with differences in fetal metabolic controls, limited cardiac reserve, and limited tissue diffusion rates in actively metabolizing tissues.

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

Multishelled CaO Microspheres Stabilized by Atomic Layer Deposition of Al2 O3 for Enhanced CO2 Capture Performance.

PubMed

Armutlulu, Andac; Naeem, Muhammad Awais; Liu, Hsueh-Ju; Kim, Sung Min; Kierzkowska, Agnieszka; Fedorov, Alexey; Müller, Christoph R

2017-11-01

CO 2 capture and storage is a promising concept to reduce anthropogenic CO 2 emissions. The most established technology for capturing CO 2 relies on amine scrubbing that is, however, associated with high costs. Technoeconomic studies show that using CaO as a high-temperature CO 2 sorbent can significantly reduce the costs of CO 2 capture. A serious disadvantage of CaO derived from earth-abundant precursors, e.g., limestone, is the rapid, sintering-induced decay of its cyclic CO 2 uptake. Here, a template-assisted hydrothermal approach to develop CaO-based sorbents exhibiting a very high and cyclically stable CO 2 uptake is exploited. The morphological characteristics of these sorbents, i.e., a porous shell comprised of CaO nanoparticles coated by a thin layer of Al 2 O 3 (<3 nm) containing a central void, ensure (i) minimal diffusion limitations, (ii) space to accompany the substantial volumetric changes during CO 2 capture and release, and (iii) a minimal quantity of Al 2 O 3 for structural stabilization, thus maximizing the fraction of CO 2 -capture-active CaO. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructural origin of semiconductivity and large magnetoresistance in epitaxial NiCo2O4/Al2O3 thin films

NASA Astrophysics Data System (ADS)

Zhen, Congmian; Zhang, XiaoZhe; Wei, Wengang; Guo, Wenzhe; Pant, Ankit; Xu, Xiaoshan; Shen, Jian; Ma, Li; Hou, Denglu

2018-04-01

Despite low resistivity (~1 mΩ cm), metallic electrical transport has not been commonly observed in inverse spinel NiCo2O4, except in certain epitaxial thin films. Previous studies have stressed the effect of valence mixing and the degree of spinel inversion on the electrical conduction of NiCo2O4 films. In this work, we studied the effect of nanostructural disorder by comparing the NiCo2O4 epitaxial films grown on MgAl2O4 (1 1 1) and on Al2O3 (0 0 1) substrates. Although the optimal growth conditions are similar for the NiCo2O4 (1 1 1)/MgAl2O4 (1 1 1) and the NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films, they show metallic and semiconducting electrical transport, respectively. Post-growth annealing decreases the resistivity of NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films, but the annealed films are still semiconducting. While the semiconductivity and the large magnetoresistance in NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films cannot be accounted for in terms of non-optimal valence mixing and spinel inversion, the presence of anti-phase boundaries between nano-sized crystallites, generated by the structural mismatch between NiCo2O4 and Al2O3, may explain all the experimental observations in this work. These results reveal nanostructural disorder as being another key factor for controlling the electrical transport of NiCo2O4, with potentially large magnetoresistance for spintronics applications.

Studies on the structural stability of Co2P2O7 under pressure

NASA Astrophysics Data System (ADS)

Wang, W. P.; Pang, H.; Jin, M. L.; Shen, X.; Yao, Y.; Wang, Y. G.; Li, Y. C.; Li, X. D.; Jin, C. Q.; Yu, R. C.

2018-05-01

The crystal structural evolution of Co2P2O7 was studied by using in situ high pressure angle dispersive x-ray diffraction with synchrotron radiation. The results demonstrate that the α phase of Co2P2O7 goes through a partially irreversible structural transformation to β phase under pressure. The pressure is conductive to reduce the longest Cosbnd O bond length of the α phase, and then more uniform Cosbnd O bonds and regular hexagonal arrangement of CoO6 octahedra of the β phase are favored. According to the Birch-Murnaghan equation, the fitted bulk modulus B0 is 158.1(±5.6) GPa for α phase and 276.5(±6.5) GPa for β phase. Furthermore, the first-principles calculations show that these two phases of Co2P2O7 have almost equal total energies, and also have similar band structures and spin-polarized density of states at their ground states. This may be the reason why these two phases of Co2P2O7 can coexist in the pressure released state. It is found that the band gap energies decrease with increasing pressure for both phases.

Comparison of simultaneous CO2 and H2O observations of Venus

NASA Technical Reports Server (NTRS)

Barker, E. S.

1975-01-01

Results are reported for 115 pairs of CO2 and H2O abundance determinations made with the coude scanner of a 2.7 m reflector. The pairs of observations were made over the same area of the illuminated disk of Venus with the guiding, seeing and slit-placement errors less than 15 per cent of the disk diameter. A correlation analysis of the pairs of observations grouping them into eight periods of time which corresponded to telescope observing runs or periods of similar phase angle shows a lack of correlation in all except one period. For this set, the H2O abundances were positively correlated with the relative CO2 line strengths for measurements of the 8689-A and 7820-A CO2 bands made on the same day. Comparison of abundances on some 25 individual days shows a positive correlation on one day and a marginal negative correlation on two days, with no correlation on the remaining 22 days. On the basis of the lack of correlations, it is concluded that either the H2O level of line formation does not fluctuate in phase with the observed CO2 absorption fluctuations or the horizontal distribution of the H2O vapor must be inhomogeneous.

Modeling Closed Equilibrium Systems of H2O-Dissolved CO2-Solid CaCO3.

PubMed

Tenno, Toomas; Uiga, Kalev; Mashirin, Alexsey; Zekker, Ivar; Rikmann, Ergo

2017-04-27

In many places in the world, including North Estonia, the bedrock is limestone, which consists mainly of CaCO 3 . Equilibrium processes in water involving dissolved CO 2 and solid CaCO 3 play a vital role in many biological and technological systems. The solubility of CaCO 3 in water is relatively low. Depending on the concentration of dissolved CO 2 , the solubility of CaCO 3 changes, which determines several important ground- and wastewater parameters, for example, Ca 2+ concentration and pH. The distribution of ions and molecules in the closed system solid H 2 O-dissolved CO 2 -solid CaCO 3 is described in terms of a structural scheme. Mathematical models were developed for the calculation of pH and concentrations of ions and molecules (Ca 2+ , CO 3 2- , HCO 3 - , H 2 CO 3 , CO 2 , H + , and OH - ) in the closed equilibrium system at different initial concentrations of CO 2 in the water phase using an iteration method. The developed models were then experimentally validated.

Interaction of SO2 and CO with the Ti2O3(101¯2) surface

NASA Astrophysics Data System (ADS)

Smith, Kevin E.; Henrich, Victor E.

1985-10-01

The interaction of sulfur dioxide with the nearly perfect (101¯2) surface of the corundum transition-metal oxide Ti2O3 has been studied using ultraviolet and x-ray photoemission spectroscopies and low-energy electron diffraction. The reaction of SO2 with Ti2O3 is found to be extremely vigorous, with SO2 adsorbing dissociatively and catalyzing the complete oxidation of the surface to TiO2 and TiS2. This result is significant since exposure to large amounts of O2 does not result in the production of large amounts of TiO2 at the Ti2O3 surface. Dissociative adsorption of SO2 continues for exposures up to at least 104 L (1 L=10-6Torr sec). The reaction is accompanied by large scale surface disorder and by an increase in the work function of 1.32 eV. In contrast, CO adsorbs molecularly for exposures >=105 L, with an extramolecular relaxation-polarization shift of 3.0 eV. For CO exposures <=104 L, the chemisorption mechanism is tentatively identified as dissociative adsorption at defect sites. Inclusive of this study, the interaction of four oxygen-containing molecules (SO2, CO, H2O, and O2) with Ti2O3(101¯2) surfaces has been studied, and their behavior is compared and trends isolated with a view to understanding the oxidation of Ti2O3.

Improvements of CO2 and O2 Transmission Modeling for ASCENDS Mission Applications

NASA Technical Reports Server (NTRS)

Pliutau, Denis; Prasad, Narashimha S.

2011-01-01

Simulations using the HITRAN database and other data have been carried out to select the optimum laser wavelengths for the measurements of CO2 and O2 concentrations with the application to the ASCENDS mission. The accuracy set forth for the ASCENDS mission requires accurate line-by-line calculations involving the use of non-Voigt line shapes. To aid in achieving this goal, improved CO2 and O2 transmission calculation methods are being developed. In particular, line-by-line transmission modeling of CO2 was improved by implementing non-Voigt spectral lineshapes. Ongoing work involves extending this approach to the O2 molecule 1.26-1.27micron spectral band.

CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study.

PubMed

Hafeez, Sarah; Fan, X; Hussain, Arshad; Martín, C F

2015-09-01

CO2 is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO2. Membrane gas separation is a fast growing CO2 capture technique, particularly gas separation by composite membranes. The separation of CO2 by a membrane is not just a process to physically sieve out of CO2 through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO2. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO2 in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO2 through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO2) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO2 membrane adsorbed more quantity of CO2 gas as compared to pure CA membrane. The high CO2 adsorption capacity may enhance the diffusion and solubility of CO2 in the CA-TiO2 composite membrane, which results in a better CO2 separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R(2), the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion. Copyright © 2015. Published by Elsevier B.V.

Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.; Sidney, Barry D.; Miller, Irvin M.; Brown, Kenneth G.; Vannorman, John D.; Schryer, Jacqueline; Brown, David R.

1990-01-01

Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.

Induction by Bradyrhizobium diazoefficiens of Different Pathways for Growth in D-mannitol or L-arabinose Leading to Pronounced Differences in CO2 Fixation, O2 Consumption, and Lateral-Flagellum Production.

PubMed

Cogo, Carolina; Pérez-Giménez, Julieta; Rajeswari, Chandrasekar B; Luna, María F; Lodeiro, Aníbal R

2018-01-01

Bradyrhizobium diazoefficiens , a soybean N 2 -fixing symbiont, constitutes the basic input in one of the most prominent inoculant industries worldwide. This bacterium may be cultured with D-mannitol or L-arabinose as carbon-plus-energy source (C-source) with similar specific growth rates, but with higher biomass production with D-mannitol. To better understand the bacterium's carbon metabolism, we analyzed, by liquid chromatography and tandem mass spectrometry (MS), the whole set of proteins obtained from cells grown on each C-source. Among 3,334 proteins identified, 266 were overproduced in D-mannitol and 237 in L-arabinose, but among these, only 22% from D-mannitol cultures and 35% from L-arabinose cultures were annotated with well defined functions. In the D-mannitol-differential pool we found 19 enzymes of the pentose-phosphate and Calvin-Benson-Bassham pathways and accordingly observed increased extracellular-polysaccharide production by D-mannitol grown bacteria in a CO 2 -enriched atmosphere. Moreover, poly-3-hydroxybutyrate biosynthesis was increased, suggesting a surplus of reducing power. In contrast, the L-arabinose-differential pool contained 11 enzymes of the L-2-keto-3-deoxyarabonate pathway, 4 enzymes for the synthesis of nicotinamide-adenine dinucleotide from aspartate, with those cultures having a threefold higher O 2 -consumption rate than the D-mannitol cultures. The stoichiometric balances deduced from the modeled pathways, however, resulted in similar O 2 consumptions and ATP productions per C-mole of substrate. These results suggested higher maintenance-energy demands in L-arabinose, which energy may be used partly for flagella-driven motility. Since B. diazoefficiens produces the lateral-flagella system in only L-arabinose, we calculated the O 2 -consumption rates of a lafR ::Km mutant devoid of lateral flagella cultured in L-arabinose or D-mannitol. Contrary to that of the wild-type, the O 2 -consumption rate of this mutant was similar on

Steady-state studies of the reactions of H2O-CO and CO2-H2 mixtures with liquid iron

NASA Astrophysics Data System (ADS)

Sasaki, Y.; Belton, G. R.

1998-08-01

Studies have been made of the steady-stata composition of liquid iron exposed to high flow rates of H2O-CO mixtures at 1550 °C to 1700 °C and CO2-H2 mixtures at 1600 °C. Values of the steady-state activity of oxygen have been established by measurement of either the carbon concentration or the silicon concentration when the iron was held in a silica crucible. Additions of sulfur or selenium to the iron have been found to result in steady-state oxygen activities, which differ significantly from those expected from water-gas equilibrium. The results are interpreted to show that the ratio of the apparent first-order rate constants for the reactions of H2O and CO2 with liquid iron is about 3 at 1600 °C. It is shown that the dependencies of the rate constants on the activities of sulfur, oxygen, and selenium must, even if complex, be similar for the H2O and CO2 reactions with liquid iron, to a good approximation.

Origin of Active Oxygen in a Ternary CuO x /Co 3O 4–CeO 2 Catalyst for CO Oxidation

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

Liu, Zhigang; Wu, Zili; Peng, Xihong

2014-11-14

In this paper, we have studied CO oxidation over a ternary CuO x/Co 3O 4-CeO 2 catalyst and employed the techniques of N 2 adsorption/desporption, XRD, TPR, TEM, in situ DRIFTS and QMS (Quadrupole mass spectrometer) to explore the origin of active oxygen. DRIFTS-QMS results with labeled 18O2 indicate that the origin of active oxygens in CuO x/Co 3O 4-CeO 2 obeys a model, called as queue mechanism. Namely gas-phase molecular oxygens are dissociated to atomic oxygens and then incorporate in oxygen vacancies located at the interface of Co 3O 4-CeO 2 to form active crystalline oxygens, and these activemore » oxygens diffuse to the CO-Cu + sites thanks to the oxygen vacancy concentration magnitude and react with the activated CO to form CO 2. This process, obeying a queue rule, provides active oxygens to form CO 2 from gas-phase O 2 via oxygen vacancies and crystalline oxygen at the interface of Co 3O 4-CeO 2.« less

Potential of SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles in achieving integrated magneto-optical isolators

NASA Astrophysics Data System (ADS)

Zamani, Mehdi; Hocini, Abdesselam

2017-05-01

We have investigated the potential of the SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles in order to overcome the problem of integration of the magneto-optical isolators (MOIs). In this way, we have performed a theoretical study for the case of designing perfect and adjustable MOIs based on magnetophotonic crystals (MPCs) containing SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles as a magnetic medium. Despite the existence the attenuation coefficient for SiO2/ZrO2 matrix at wavelength 1550 nm that leads to a non-perfect transmittance, we could introduce an MPC structure having no reflectance; therefore, an ideal MOI for eliminating unwanted back-reflection could be achieved.

MEMS-Based Gas Sensor Using PdO-Decorated TiO2 Thin Film for Highly Sensitive and Selective H2 Detection with Low Power Consumption

NASA Astrophysics Data System (ADS)

Kwak, Seungmin; Shim, Young-Seok; Yoo, Yong Kyoung; Lee, Jin-Hyung; Kim, Inho; Kim, Jinseok; Lee, Kyu Hyoung; Lee, Jeong Hoon

2018-03-01

We report a micromachined H2 sensor that is composed of a Pt micro-heater, low-stress insulating layer (SiO2/SiNx/SiO2), Pt-interdigitated electrodes, and gas sensing materials. Three types of Pt micro-heater are designed as function of electrode width, and their thermal properties are systematically analyzed by finite element modeling FEM with infrared camera. The power consumptions when the surface temperature reached 150, 200, 250, and 300 °C are calculated to approximately 33, 48, 67 and 85 mW, respectively. The response of the PdO nanoparticles-decorated TiO2 thin films to H2 is much higher than those of other gases such as CH4 and CO at 200 °C (48 mW). Further, the response time is reduced to approximately 3 s. The enhancement of gas sensing properties is related to well-designed micro-heater and catalytic effects of PdO nanoparticles such as electronic and chemical sensitization. These results suggest that the PdO nanoparticles-decorated TiO2 thin film, namely MEMS-based H2 sensors are very promising for use in IoT application to improve the quality of human's life.

MEMS-Based Gas Sensor Using PdO-Decorated TiO2 Thin Film for Highly Sensitive and Selective H2 Detection with Low Power Consumption

NASA Astrophysics Data System (ADS)

Kwak, Seungmin; Shim, Young-Seok; Yoo, Yong Kyoung; Lee, Jin-Hyung; Kim, Inho; Kim, Jinseok; Lee, Kyu Hyoung; Lee, Jeong Hoon

2018-05-01

We report a micromachined H2 sensor that is composed of a Pt micro-heater, low-stress insulating layer (SiO2/SiNx/SiO2), Pt-interdigitated electrodes, and gas sensing materials. Three types of Pt micro-heater are designed as function of electrode width, and their thermal properties are systematically analyzed by finite element modeling FEM with infrared camera. The power consumptions when the surface temperature reached 150, 200, 250, and 300 °C are calculated to approximately 33, 48, 67 and 85 mW, respectively. The response of the PdO nanoparticles-decorated TiO2 thin films to H2 is much higher than those of other gases such as CH4 and CO at 200 °C (48 mW). Further, the response time is reduced to approximately 3 s. The enhancement of gas sensing properties is related to well-designed micro-heater and catalytic effects of PdO nanoparticles such as electronic and chemical sensitization. These results suggest that the PdO nanoparticles-decorated TiO2 thin film, namely MEMS-based H2 sensors are very promising for use in IoT application to improve the quality of human's life.

Enhanced performance of CO oxidation over Pt/CuCrOx catalyst in the presence of CO2 and H2O

NASA Astrophysics Data System (ADS)

Deng, Yun; Wang, Ting; Zhu, Li; Jia, Ai-Pin; Lu, Ji-Qing; Luo, Meng-Fei

2018-06-01

A Pt catalyst supported on CuO-CrOx composite oxide (Pt/CuCrOx) was prepared and tested for CO oxidation in the presence of CO2 and H2O. It was found that the catalyst was stable in the realistic reaction conditions and the catalytic activity was improved in the presence of CO2 and H2O compared to that in dry condition. Kinetic investigation and temperature - programmed desorption of CO results revealed that the addition of CO2 in the feed resulted in the competitive adsorption of CO/CO2 and the formation of surface carbonate species, which consequently deactivated the catalyst. In contrast, although the presence of H2O also inhibited the adsorption of CO, the possible formation of surface hydroxyl groups may trigger a new and more facile reaction route for CO oxidation, which could explain the promoting effect of H2O. Therefore, the current findings makes the catalyst promising in CO oxidation under realistic reaction conditions.

Using the Relationship between Vehicle Fuel Consumption and CO[subscript 2] Emissions to Illustrate Chemical Principles

ERIC Educational Resources Information Center

Oliver-Hoyo, Maria T.; Pinto, Gabriel

2008-01-01

This instructional resource utilizes consumer product information by which students compare theoretical stoichiometric calculations to CO[subscript 2] car emissions and fuel consumption data. Representing graphically the emission of CO[subscript 2] versus consumption of fuel provides a tangible way of connecting concepts studied in chemistry…

Study on O2 generation and CO2 absorption capability of four co-cultured salad plants in an enclosed system

NASA Astrophysics Data System (ADS)

Guo, Shuangsheng; Ai, Weidang; Tang, Yongkang; Cheng, Quanyong; Shen, Yunze; Qin, Lifeng; Ma, Jialu; Zhu, Jingtao; Ren, Jin

2014-06-01

The ability to generate O2 and absorb CO2 of several co-cultured vegetable plants in an enclosed system was studied to provide theoretical reference for the future man-plant integrated tests. Four kinds of salad plants (Lactuca sativa L. var. Dasusheng, Lactuca sativa L. var. Youmaicai, Gynura bicolor and Cichorium endivia L.) were grown in the CELSS Integration Test Platform (CITP). The environmental factors including O2 and CO2 concentration were continuously monitored on-line and the plant biomass was measured at the end of the test. The changing rules of O2 and CO2 concentration in the system were basically understood and it was found that the O2 generated by the plants could satisfy the respiratory needs of 1.75 persons by calculation. It was also found that the plants could absorb the CO2 breathed out by 2 persons when the light intensity was raised to 550 mmol m-2 s-1 PPF. The results showed that the co-cultured plants hold good compatibility and excellent O2-generating and CO2-absorbing capability. They could also supply some fresh edible vegetable for a 2-person crew.

Hierarchical NiCo2O4 Hollow Sphere as a Peroxidase Mimetic for Colorimetric Detection of H2O2 and Glucose

PubMed Central

Huang, Wei; Lin, Tianye; Cao, Yang; Lai, Xiaoyong; Peng, Juan; Tu, Jinchun

2017-01-01

In this work, the hierarchical NiCo2O4 hollow sphere synthesized via a “coordinating etching and precipitating” process was demonstrated to exhibit intrinsic peroxidase-like activity. The peroxidase-like activity of NiCo2O4, NiO, and Co3O4 hollow spheres were comparatively studied by the catalytic oxidation reaction of 3,3,5,5-tetramethylbenzidine (TMB) in presence of H2O2, and a superior peroxidase-like activity of NiCo2O4 was confirmed by stronger absorbance at 652 nm. Furthermore, the proposed sensing platform showed commendable response to H2O2 with a linear range from 10 μM to 400 μM, and a detection limit of 0.21 μM. Cooperated with GOx, the developed novel colorimetric and visual glucose-sensing platform exhibited high selectivity, favorable reproducibility, satisfactory applicability, wide linear range (from 0.1 mM to 4.5 mM), and a low detection limit of 5.31 μM. In addition, the concentration-dependent color change would offer a better and handier way for detection of H2O2 and glucose by naked eye. PMID:28124997

Airborne testing and demonstration of a new flight system based on an Aerodyne N2O-CO2-CO-H2O mini-spectrometer

NASA Astrophysics Data System (ADS)

Gvakharia, A.; Kort, E. A.; Smith, M. L.; Conley, S.

2017-12-01

Nitrous oxide (N2O) is a powerful greenhouse gas and ozone depleting substance. With high atmospheric backgrounds and small relative signals, N2O emissions have been challenging to observe and understand on regional scales with traditional instrumentation. Fast-response airborne measurements with high precision and accuracy can potentially bridge this observational gap. Here we present flight assessments of a new flight system based on an Aerodyne mini-spectrometer as well as a Los Gatos N2O/CO analyzer during the Fertilizer Emissions Airborne Study (FEAST). With the Scientific Aviation Mooney aircraft, we conducted test flights for both analyzers where a known calibration gas was sampled throughout the flight (`null' tests). Clear altitude/cabin-pressure dependencies were observed for both analyzers if operated in an "off-the-shelf' manner. For the remainder of test flights and the FEAST campaign we used a new flight system based on an Aerodyne mini-spectrometer with the addition of a custom pressure control/calibration system. Instead of using traditional approaches with spectral-zeros and infrequent in-flight calibrations, we employ a high-flow system with stable flow control to enable high frequency (2 minutes), short duration (15 seconds) sampling of a known calibration gas. This approach, supported by the null test, enables correction for spectral drift caused by a variety of factors while maintaining a 90% duty cycle for 1Hz sampling from an aircraft. Preliminary in-flight precisions are estimated at 0.05 ppb, 0.1 ppm, 1 ppb, and 10 ppm for N2O, CO2, CO, and H2O respectively. We also present a further 40 hours of inter-comparison in flight with a Picarro 2301-f ring-down spectrometer demonstrating consistency between CO2 and H2O measurements and no altitude dependent error.

CaO-Based CO2 Sorbents Effectively Stabilized by Metal Oxides.

PubMed

Naeem, Muhammad Awais; Armutlulu, Andac; Imtiaz, Qasim; Müller, Christoph R

2017-11-17

Calcium looping (i.e., CO 2 capture by CaO) is a promising second-generation CO 2 capture technology. CaO, derived from naturally occurring limestone, offers an inexpensive solution, but due to the harsh operating conditions of the process, limestone-derived sorbents undergo a rapid capacity decay induced by the sintering of CaCO 3 . Here, we report a Pechini method to synthesize cyclically stable, CaO-based CO 2 sorbents with a high CO 2 uptake capacity. The sorbents synthesized feature compositional homogeneity in combination with a nanostructured and highly porous morphology. The presence of a single (Al 2 O 3 or Y 2 O 3 ) or bimetal oxide (Al 2 O 3 -Y 2 O 3 ) provides cyclic stability, except for MgO which undergoes a significant increase in its particle size with the cycle number. We also demonstrate a direct relationship between the CO 2 uptake and the morphology of the synthesized sorbents. After 30 cycles of calcination and carbonation, the best performing sorbent, containing an equimolar mixture of Al 2 O 3 and Y 2 O 3 , exhibits a CO 2 uptake capacity of 8.7 mmol CO 2  g -1 sorbent, which is approximately 360 % higher than that of the reference limestone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micropore Formation of [Zn2(Oxac) (Taz)2]·(H2O)2.5 via CO2 Adsorption.

PubMed

Zubir, Moondra; Hamasaki, Atom; Iiyama, Taku; Ohta, Akira; Ohki, Hiroshi; Ozeki, Sumio

2017-01-24

As-synthesized [Zn 2 (Oxac) (Taz) 2 ]·(H 2 O) 2.5 , referred to as ZOTW 2.5 , was prepared from aqueous methanol solutions of Zn 5 (CO 3 ) 2 (OH) 6 and two kinds of ligands of 1,2,4-triazole (Taz) and oxalic acid (Oxac) at 453 K for 12 h. The crystal structure was determined by the Rietveld method. As-synthesized ZOTW 2.5 was pretreated at 383 K and 1 mPa for t pt h, ZOTW x (t pt h). ZOTW x (≥3h) showed a type I adsorption isotherm for N 2 at 77 K having a saturation amount (V s ) of 180 mg/g, but that pretreated shortly showed only 1/10 in V s . CO 2 was adsorbed at 303 K in sigmoid on nonporous ZOTW x (≤2h) and in Langmuir-type on ZOTW x (≥3h) to reach the adsorption amount of 120 mg/g at 700 Torr. N 2 adsorption on ZOTW x (≤2h)deCO 2 , degassed after CO 2 adsorption on ZOTW x (≤2h), was promoted 5-fold from 180 mg/g on ZOTW x (t pt h) and ZOTW x (≥3h)deCO 2 up to ca. 1000 mg/g. The interaction of CO 2 and H 2 O molecules in micropores may lead to a new route for micropore formation.

TiO2@PEI-Grafted-MWCNTs Hybrids Nanocomposites Catalysts for CO2 Photoreduction

PubMed Central

Falcicchio, Aurelia; Fracassi, Francesco; Margiotta, Valerio; Moliterni, Anna

2018-01-01

Anatase (TiO2) and multiwalled carbon nanotubes bearing polyethylenimine (PEI) anchored on their surface were hybridized in different proportions according to a sol-gel method. The resulting nanocomposites (TiO2@PEI-MWCNTs), characterized by BET, XRD, XPS, SEM, and UV techniques, were found efficient catalysts for CO2 photoreduction into formic and acetic acids in water suspension and under visible light irradiation. PEI-grafted nanotubes co-catalysts are believed to act as CO2 activators by forming a carbamate intermediate allowing to accomplish the first example in the literature of polyamines/nanotubes/TiO2 mediated CO2 photoreduction to carboxylic acids. PMID:29461484

Optimization of intermolecular potential parameters for the CO2/H2O mixture.

PubMed

Orozco, Gustavo A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

2014-10-02

Monte Carlo simulations in the Gibbs ensemble were used to obtain optimized intermolecular potential parameters to describe the phase behavior of the mixture CO2/H2O, over a range of temperatures and pressures relevant for carbon capture and sequestration processes. Commonly used fixed-point-charge force fields that include Lennard-Jones 12-6 (LJ) or exponential-6 (Exp-6) terms were used to describe CO2 and H2O intermolecular interactions. For force fields based on the LJ functional form, changes of the unlike interactions produced higher variations in the H2O-rich phase than in the CO2-rich phase. A major finding of the present study is that for these potentials, no combination of unlike interaction parameters is able to adequately represent properties of both phases. Changes to the partial charges of H2O were found to produce significant variations in both phases and are able to fit experimental data in both phases, at the cost of inaccuracies for the pure H2O properties. By contrast, for the Exp-6 case, optimization of a single parameter, the oxygen-oxygen unlike-pair interaction, was found sufficient to give accurate predictions of the solubilities in both phases while preserving accuracy in the pure component properties. These models are thus recommended for future molecular simulation studies of CO2/H2O mixtures.

MgO-based adsorbents for CO2 adsorption: Influence of structural and textural properties on the CO2 adsorption performance.

PubMed

Elvira, Gutiérrez-Bonilla; Francisco, Granados-Correa; Víctor, Sánchez-Mendieta; Alberto, Morales-Luckie Raúl

2017-07-01

A series of MgO-based adsorbents were prepared through solution-combustion synthesis and ball-milling process. The prepared MgO-based powders were characterized using X-ray diffraction, scanning electron microscopy, N 2 physisorption measurements, and employed as potential adsorbents for CO 2 adsorption. The influence of structural and textural properties of these adsorbents over the CO 2 adsorption behaviour was also investigated. The results showed that MgO-based products prepared by solution-combustion and ball-milling processes, were highly porous, fluffy, nanocrystalline structures in nature, which are unique physico-chemical properties that significantly contribute to enhance their CO 2 adsorption. It was found that the MgO synthesized by solution combustion process, using a molar ratio of urea to magnesium nitrate (2:1), and treated by ball-milling during 2.5hr (MgO-BM2.5h), exhibited the maximum CO 2 adsorption capacity of 1.611mmol/g at 25°C and 1atm, mainly via chemisorption. The CO 2 adsorption behaviour on the MgO-based adsorbents was correlated to their improved specific surface area, total pore volume, pore size distribution and crystallinity. The reusability of synthesized MgO-BM2.5h was confirmed by five consecutive CO 2 adsorption-desorption times, without any significant loss of performance, that supports the potential of MgO-based adsorbent. The results confirmed that the special features of MgO prepared by solution-combustion and treated by ball-milling during 2.5hr are favorable to be used as effective MgO-based adsorbent in post-combustion CO 2 capture technologies. Copyright © 2016. Published by Elsevier B.V.

Surface modification of layered perovskite Sr2TiO4 for improved CO2 photoreduction with H2O to CH4.

PubMed

Kwak, Byeong Sub; Do, Jeong Yeon; Park, No-Kuk; Kang, Misook

2017-11-27

Layered perovskite Sr 2 TiO 4 photocatalyst was synthesized by using sol-gel method with citric acid. In order to increase the surface area of layered perovskite Sr 2 TiO 4 , and thus to improve its photocatalytic activity for CO 2 reduction, its surface was modified via hydrogen treatment or exfoliation. The physical and chemical properties of the prepared catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, elemental mapping analysis, energy-dispersive X-ray spectroscopy, N 2 adsorption-desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electrophoretic light scattering. CO 2 photoreduction was performed in a closed reactor under 6 W/cm 2 UV irradiation. The gaseous products were analyzed using a gas chromatograph equipped with flame ionization and thermal conductivity detectors. The exfoliated Sr 2 TiO 4 catalyst (E-Sr 2 TiO 4 ) exhibited a narrow band gap, a large surface area, and high dispersion. Owing to these advantageous properties, E-Sr 2 TiO 4 photocatalyst showed an excellent catalytic performance for CO 2 photoreduction reaction. The rate of CH 4 production from the photoreduction of CO 2 with H 2 O using E-Sr 2 TiO 4 was about 3431.77 μmol/g cat after 8 h.

Dynamic impact of urbanization, economic growth, energy consumption, and trade openness on CO 2 emissions in Nigeria.

PubMed

Ali, Hamisu Sadi; Law, Siong Hook; Zannah, Talha Ibrahim

2016-06-01

The objective of this paper is to examine the dynamic impact of urbanization, economic growth, energy consumption, and trade openness on CO 2 emissions in Nigeria based on autoregressive distributed lags (ARDL) approach for the period of 1971-2011. The result shows that variables were cointegrated as null hypothesis was rejected at 1 % level of significance. The coefficients of long-run result reveal that urbanization does not have any significant impact on CO 2 emissions in Nigeria, economic growth, and energy consumption has a positive and significant impact on CO 2 emissions. However, trade openness has negative and significant impact on CO 2 emissions. Consumption of energy is among the main determinant of CO 2 emissions which is directly linked to the level of income. Despite the high level of urbanization in the country, consumption of energy still remains low due to lower income of the majority populace and this might be among the reasons why urbanization does not influence emissions of CO 2 in the country. Initiating more open economy policies will be welcoming in the Nigerian economy as the openness leads to the reduction of pollutants from the environment particularly CO 2 emissions which is the major gases that deteriorate physical environment.

Heterogeneous UV/Fenton degradation of bisphenol A catalyzed by synergistic effects of FeCo2O4/TiO2/GO.

PubMed

Bai, Xue; Lyu, Lingling; Ma, Wenqiang; Ye, Zhengfang

2016-11-01

A new method for bisphenol A (BPA) degradation in aqueous solution was developed. The characteristics of BPA degradation in a heterogeneous ultraviolet (UV)/Fenton reaction catalyzed by FeCo 2 O 4 /TiO 2 /graphite oxide (GO) were studied. The properties of the synthesized catalysts were characterized using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. FeCo 2 O 4 and TiO 2 were grown as spherical shape, rough surface, and relatively uniform on the surface of GO (FeCo 2 O 4 /TiO 2 /GO). Batch tests were conducted to evaluate the effects of the initial pH, FeCo 2 O 4 /TiO 2 /GO dosage, and H 2 O 2 concentration on BPA degradation. In a system with 0.5 g L -1 of FeCo 2 O 4 /TiO 2 /GO and 10 mmol L -1 of H 2 O 2 , approximately 90 % of BPA (20 mg L -1 ) was degraded within 240 min of UV irradiation at pH 6.0. The reused FeCo 2 O 4 /TiO 2 /GO catalyst retained its activity after three cycles, which indicates that it is stable and reusable. The heterogeneous UV/Fenton reaction catalyzed by FeCo 2 O 4 /TiO 2 /GO is a promising advanced oxidation technology for treating wastewater that contains BPA.

Oxygen Vacancies in ZnO Nanosheets Enhance CO2 Electrochemical Reduction to CO.

PubMed

Geng, Zhigang; Kong, Xiangdong; Chen, Weiwei; Su, Hongyang; Liu, Yan; Cai, Fan; Wang, Guoxiong; Zeng, Jie

2018-05-22

As electron transfer to CO 2 is generally considered to be the critical step during the activation of CO 2 , it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO 2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO 2 activation by introducing oxygen vacancies into electrocatalysts with electronic-rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of -16.1 mA cm -2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO 2 . Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO 2 and the eased CO 2 activation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

2012-10-28

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

The relationship between economic growth, energy consumption, and CO2 emissions: Empirical evidence from China.

PubMed

Wang, Shaojian; Li, Qiuying; Fang, Chuanglin; Zhou, Chunshan

2016-01-15

Following several decades of rapid economic growth, China has become the largest energy consumer and the greatest emitter of CO2 in the world. Given the complex development situation faced by contemporary China, Chinese policymakers now confront the dual challenge of reducing energy use while continuing to foster economic growth. This study posits that a better understanding of the relationship between economic growth, energy consumption, and CO2 emissions is necessary, in order for the Chinese government to develop the energy saving and emission reduction strategies for addressing the impacts of climate change. This paper investigates the cointegrating, temporally dynamic, and casual relationships that exist between economic growth, energy consumption, and CO2 emissions in China, using data for the period 1990-2012. The study develops a comprehensive conceptual framework in order to perform this analysis. The results of cointegration tests suggest the existence of long-run cointegrating relationship among the variables, albeit with short dynamic adjustment mechanisms, indicating that the proportion of disequilibrium errors that can be adjusted in the next period will account for only a fraction of the changes. Further, impulse response analysis (which describes the reaction of any variable as a function of time in response to external shocks) found that the impact of a shock in CO2 emissions on economic growth or energy consumption was only marginally significant. Finally, Granger casual relationships were found to exist between economic growth, energy consumption, and CO2 emissions; specifically, a bi-directional causal relationship between economic growth and energy consumption was identified, and a unidirectional causal relationship was found to exist from energy consumption to CO2 emissions. The findings have significant implications for both academics and practitioners, warning of the need to develop and implement long-term energy and economic policies in

Reactivity of a Thick BaO Film Supported on Pt(111): Adsorption and Reaction of NO2, H2O and CO2

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

Mudiyanselage, Kumudu; Yi, Cheol-Woo W.; Szanyi, Janos

2009-09-15

Reactions of NO2, H2O, and CO2 with a thick (> 20 MLE) BaO film supported on Pt(111) were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). NO2 reacts with a thick BaO to form surface nitrite-nitrate ion pairs at 300 K, while only nitrates form at 600 K. In the thermal decomposition process of nitrite–nitrate ion pairs, first nitrites decompose and desorb as NO. Then nitrates decompose in two steps : at lower temperature with the release of NO2 and at higher temperature, nitrates dissociate to NO + O2. The thick BaO layer converts completely to Ba(OH)2more » following the adsorption of H2O at 300 K. Dehydration/dehydroxylation of this hydroxide layer can be fully achieved by annealing to 550 K. CO2 also reacts with BaO to form BaCO3 that completely decomposes to regenerate BaO upon annealing to 825 K. However, the thick BaO film cannot be converted completely to Ba(NOx)2 or BaCO3 under the experimental conditions employed in this study.« less

Behavior of Al2O3 and SiO2 with heating in a Cl2 + CO stream

NASA Technical Reports Server (NTRS)

Shchetinin, L. K.

1984-01-01

Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA) were used to study the chlorination of alpha-Al2O3, gamma-Al2O3 and amorphous SiO2 in a Cl + CO stream, for the preparation of AlCl3 and SiCl4. The chlorination starting temperatures were 235 deg for Al2O3 and 680 deg for SiO2. The chlorination of alpha- and gamma-Al2O3 takes place via the formation of AlOCl as an intermediate product, and its subsequent dissociation at 480 to 560 deg, according to 3AlOCl yields AlCl3 + Al2O3. The chlorination activation energies are given for the three oxides.

Following 18O uptake in scCO2–H2O mixtures with Raman spectroscopy