El bioclima humano en urbes del sur de México para condiciones de duplicación de CO2 atmosférico

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Adalberto Tejeda Martínez

2012-02-01

Full Text Available . A partir del concepto de temperatura efectiva (TE, se presenta un escenario de las condiciones de bioclima humano de ocho ciudades importantes del sur de México, obtenido de predicciones regionales de modelos de circulación general para el caso de una duplicación en la concentración atmosférica global de CO2. Los resultados se ilustran con gráficas de las condiciones de confort actuales y futuras para el sur del país. Se encontró que, pese a los procesos de aclimatación, se intensificarán las sensaciones cálidas debido al efecto invernadero. Combinando lo anterior con proyecciones conservadoras del incremento de la población para la segunda mitad del siglo XXI, se estima que las ciudades de clima cálido quintuplicarán las necesidades de enfriamiento para obtener el confort de sus habitantes.

The surface chemistry of Cu in the presence of CO2 and H2O

Energy Technology Data Exchange (ETDEWEB)

Deng, Xingyi; Verdaguer, Albert; Herranz, Tirma; Weis, Christoph; Bluhm, Hendrik; Salmeron, Miquel

2008-07-16

The chemical nature of copper and copper oxide (Cu{sub 2}O) surfaces in the presence of CO{sub 2} and H{sub 2}O at room temperature was investigated using ambient pressure x-ray photoelectron spectroscopy. The studies reveal that in the presence of 0.1 torr CO{sub 2} several species form on the initially clean Cu, including carbonate CO{sub 3}{sup 2}, CO{sub 2}{sup {delta}-} and C{sup 0}, while no modifications occur on an oxidized surface. The addition of 0.1 ML Zn to the Cu results in the complete conversion of CO{sub 2}{sup {delta}-} to carbonate. In a mixture of 0.1 torr H{sub 2}O and 0.1 torr CO{sub 2}, new species are formed, including hydroxyl, formate and methoxy, with H{sub 2}O providing the hydrogen needed for the formation of hydrogenated species.

Soil surface CO2 fluxes and the carbon budget of a grassland

Science.gov (United States)

Norman, J. M.; Garcia, R.; Verma, S. B.

1992-01-01

Measurements of soil surface CO2 fluxes are reported for three sites within the First International Satellite Land Surface Climatology Project (ISLSCP) Field Experiment (FIFE) area, and simple empirical equations are fit to the data to provide predictions of soil fluxes from environmental observations. A prototype soil chamber, used to make the flux measurements, is described and tested by comparing CO2 flux measurements to a 40-L chamber, a 1-m/cu chamber, and eddy correlation. Results suggest that flux measurements with the prototype chamber are consistent with measurements by other methods to within about 20 percent. A simple empirical equation based on 10-cm soil temperature, 0- to 10-cm soil volumetric water content, and leaf area index predicts the soil surface CO2 flux with a rms error of 1.2 micro-mol sq m/s for all three sites. Further evidence supports using this equation to evaluate soil surface CO2 during the 1987 FIFE experiment. The soil surface CO2 fluxes when averaged over 24 hours are comparable to daily gross canopy photosynthetic rates. For 6 days of data the net daily accumulation of carbon is about 0.6 g CO2 sq m/d; this is only a few percent of the daily gross accumulation of carbon by photosynthesis. As the soil became drier in 1989, the net accumulation of carbon by the prairie increased, suggesting that the soil flux is more sensitive to temperature and drought than the photosynthetic fluxes.

Effet de la rugosité de surface sur les performances du contact ...

African Journals Online (AJOL)

Effet de la rugosité de surface sur les performances du contact segment- chemise dans un moteur à combustion interne. The effect of surface roughness on the performances of liner-piston ring contact in internal combustion engine. Amar Ayad. *. , Amar Skendraoui & Ammar Haiahem. Laboratoire de Mécanique Industrielle ...

X-ray photoelectron spectroscopy study of CO2 reaction with polycrystalline uranium surface

International Nuclear Information System (INIS)

Liu Kezhao; Yu Yong; Zhou Juesheng; Wu Sheng; Wang Xiaolin; Fu Yibei

1999-10-01

The adsorption of CO 2 on 'clean' depleted polycrystalline uranium metal surface has been studied by X-ray photoelectron spectroscopy (XPS) at 300 K. The 'clean' surface were prepared by Ar + ion sputtering under ultra-high vacuum (UHV) condition with a base pressure 6.7 x 10 -8 Pa. The result s shows that adsorption of CO 2 on 'clean' uranium metal took place in total dissociation, and leads to the formation of uranium dioxide, uranium carbides and free carbon. The total dissociation of CO 2 produced carbon, oxygen species, CO 2 2- and CO 3 2- species. The diffusion tendency of carbon was much stronger than that of oxygen, and led to form a carbide in oxide-metal interface while the oxygen remained on their surface as an oxide

A density functional theory study of the adsorption behaviour of CO{sub 2} on Cu{sub 2}O surfaces

Energy Technology Data Exchange (ETDEWEB)

Mishra, Abhishek Kumar, E-mail: akmishra@ddn.upes.ac.in, E-mail: abhishek.mishra@ucl.ac.uk, E-mail: deleeuwn@cardiff.ac.uk [Research & Development, University of Petroleum and Energy Studies (UPES), Bidholi, Dehradun 248007 (India); Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Roldan, Alberto [School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom); Leeuw, Nora H. de, E-mail: akmishra@ddn.upes.ac.in, E-mail: abhishek.mishra@ucl.ac.uk, E-mail: deleeuwn@cardiff.ac.uk [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom)

2016-07-28

Copper has many applications, particularly in electro-catalysis, where the oxidation state of the copper electrode plays a significant role in the selectivity towards products. Although copper-based materials have clear potential as catalysts in the reduction of CO{sub 2} and conversion to products, fundamental understanding of CO{sub 2} adsorption and activation on different copper oxide surfaces is still limited. We have used DFT+U methodology to study the surface reconstruction of the three most exposed (111), (110), and (001) surfaces of Cu{sub 2}O with different possible terminations. Considering several adsorbate geometries, we have investigated CO{sub 2} adsorption on five different possible terminations and proposed eight different configurations in which CO{sub 2} binds with the surface. Similar to earlier findings, CO{sub 2} binds weakly with the most stable Cu{sub 2}O(111):O surface showing no molecular activation, whereas a number of other surfaces, which can appear in the Cu{sub 2}O particles morphology, show stronger binding as well as activation of the CO{sub 2} molecule. Different CO{sub 2} coverages were studied and a detailed structural and electronic charge analysis is presented. The activation of the CO{sub 2} molecule is characterized by structural transformations and charge transfer between the surface and the CO{sub 2} molecule, which is further confirmed by considerable red shifts in the vibrational frequencies.

Reactivity of dissolved- vs. supercritical-CO2 phase toward muscovite basal surfaces

Science.gov (United States)

Wan, J.; Tokunaga, T. K.; Kim, Y.; Wang, S.; Altoe, M. V. P.; Ashby, P. D.; DePaolo, D.

2015-12-01

The current understanding of geochemical reactions in reservoirs for geological carbon sequestration (GCS) is largely based on aqueous chemistry (CO2 dissolves in reservoir brine and brine reacts with rocks). However, only a portion of the injected supercritical (sc) CO2 dissolves before the buoyant plume contacts caprock, where it is expected to reside for a long time. Although numerous studies have addressed scCO2-mineral reactions occurring within adsorbed aqueous films, possible reactions resulting from direct CO2-rock contact remain less understood. Does CO2 as a supercritical phase react with reservoir rocks? Do mineral react differently with scCO2 than with dissolved CO2? We selected muscovite, one of the more stable and common rock-forming silicate minerals, to react with scCO2 phase (both water-saturated and water-free) and compared with CO2-saturated-brine. The reacted basal surfaces were analyzed using atomic force microscopy and X-ray photoelectron spectroscopy for examining the changes in surface morphology and chemistry. The results show that scCO2 (regardless of its water content) altered muscovite considerably more than CO2-saturated brine; suggest CO2 diffusion into mica interlayers and localized mica dissolution into scCO2 phase. The mechanisms underlying these observations and their implications for GCS need further exploration.

Surface modification and enhanced photocatalytic CO{sub 2} reduction performance of TiO{sub 2}: a review

Energy Technology Data Exchange (ETDEWEB)

Low, Jingxiang; Cheng, Bei [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

2017-01-15

Highlights: • Application of modified TiO{sub 2} for photocatalytic CO{sub 2} reduction is summarized. • Different surface modification strategies of TiO{sub 2} are highlighted. • Summary and future perspectives in photocatalytic CO{sub 2} reduction are presented. - Abstract: Recently, the excessive consumption of fossil fuels has caused high emissions of the greenhouse gases, CO{sub 2} into atmosphere and global energy crisis. Mimicking the natural photosynthesis by using semiconductor materials to achieve photocatalytic CO{sub 2} reduction into valuable solar fuels such as CH{sub 4}, HCO{sub 2}H, CH{sub 2}O, and CH{sub 3}OH is known as one of the best solutions for addressing the aforementioned issue. Among various proposed photocatalysts, TiO{sub 2} has been extensively studied over the past several decades for photocatalytic CO{sub 2} reduction because of its cheapness and environmental friendliness. Particularly, surface modification of TiO{sub 2} has attracted numerous interests due to its capability of enhancing the light absorption ability, facilitating the electron-hole separation, tuning the CO{sub 2} reduction selectivity and increasing the CO{sub 2} adsorption and activation ability of TiO{sub 2} for photocatalytic CO{sub 2} reduction. In this review, recent approaches of the surface modification of TiO{sub 2} for photocatalytic CO{sub 2} reduction, including impurity doping, metal deposition, alkali modification, heterojunction construction and carbon-based material loading, are presented. The photocatalytic CO{sub 2} reduction mechanism and pathways of TiO{sub 2} are discussed. The future research direction and perspective of photocatalytic CO{sub 2} reduction over surface-modified TiO{sub 2} are also presented.

A TPD-MS study of glassy carbon surfaces oxidized by CO2 and O2

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MILA D. LAUSEVIC

2002-11-01

Full Text Available The temperature-programmed desorption (TPD method combined with mass spectrometric (MS analysis has been applied to investigate the surface properties of carbon materials. The apparatus consisting of a temperature-programmed furnace and a quadrupole mass spectrometer was constructed in order to characterize the surface of differently treated glassy carbon samples. In this work, samples of glassy carbon exposed to air, CO2 and O2 were examined. The desorption of H2O, CO and CO2, as major products, indicated the presence of different oxide groups. The amount of these groups for all samples was calculated. It is concluded that oxidation affects the nature and the amount of the surface oxide groups and contributes to their increased stability.

Spatio-temporal Variability in Surface Ocean pCO2 Inferred from Observations

OpenAIRE

Jones, Steve

2012-01-01

The variability of surface ocean pCO2 is examined on multiple spatial and temporal scales. Temporal autocorrelation analysis is used to examine pCO2 variability over multiple years. Spatial autocorrelation analysis describes pCO2 variability over multiple spatial scales. Spatial autocorrelation lengths range between

Geochemical Study of Natural CO2 Emissions in the French Massif Central: How to Predict Origin, Processes and Evolution of CO2 Leakage Étude géochimique des émissions naturelles de CO2 du Massif Central : origine et processus de migration du gaz

Directory of Open Access Journals (Sweden)

Battani A.

2010-05-01

Full Text Available This study presents an overview of some results obtained within the French ANR (National Agency of Research supported Géocarbone-Monitoring research program. The measurements were performed in Sainte-Marguerite, located in the French Massif Central. This site represents a natural laboratory for CO2/fluid/rock interactions studies, as well as CO2 migration mechanisms towards the surface. The CO2 leaking character of the studied area also allows to test and validate measurements methods and verifications for the future CO2 geological storage sites. During these surveys, we analyzed soil CO2 fluxes and concentrations. We sampled and analyzed soil gases, and gas from carbo-gaseous bubbling springs. A one-month continuous monitoring was also tested, to record the concentration of CO2 both in atmosphere and in the soil at a single point. We also developed a new methodology to collect soil gas samples for noble gas abundances and isotopic analyses, as well as carbon isotopic ratios. Our geochemical results, combined with structural geology, show that the leaking CO2 has a very deep origin, partially mantle derived. The gas rises rapidly along normal and strike-slip active faults. CO2 soil concentrations (also showing a mantle derived component and CO2 fluxes are spatially variable, and reach high values. The recorded atmospheric CO2 is not very high, despite the important CO2 degassing throughout the whole area. Cette étude présente les principaux résultats de campagnes de monitoring géochimique menées en 2006 et 2007 dans le cadre du projet Géocarbone-Monitoring, sur le site de Sainte-Marguerite, situé dans le Massif Central. Ce site constitue un « laboratoire naturel » pour l’étude des interactions CO2/fluides/roches et des mécanismes de migration du CO2 vers la surface, à l’échelle des temps géologiques. Le caractère particulièrement émissif de cet « analogue » permet également de tester et valider des méthodes de mesure et

Topological surface Fermi arcs in the magnetic Weyl semimetal Co3Sn2S2

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Xu, Qiunan; Liu, Enke; Shi, Wujun; Muechler, Lukas; Gayles, Jacob; Felser, Claudia; Sun, Yan

2018-06-01

Very recently, the half-metallic compound Co3Sn2S2 was proposed to be a magnetic Weyl semimetal (WSM) with Weyl points only 60 meV above the Fermi level EF. Owing to the low charge carrier density and large Berry curvature induced, Co3Sn2S2 possesses both a large anomalous Hall conductivity and a large anomalous Hall angle, which provide strong evidence for the existence of Weyl points in Co3Sn2S2 . In this work, we theoretically study the surface topological feature of Co3Sn2S2 and its counterpart Co3Sn2Se2 . By cleaving the sample at the weak Sn-S/Se bonds, one can achieve two different surfaces terminated with Sn and S/Se atoms, respectively. The resulting Fermi-arc-related states can range from the energy of the Weyl points to EF-0.1 eV in the Sn-terminated surface. Therefore, it should be possible to observe the Fermi arcs in angle-resolved photoemission spectroscopy (ARPES) measurements. Furthermore, in order to simulate quasiparticle interference in scanning tunneling microscopy (STM) measurements, we also calculate the joint density of states for both terminals. This work should be helpful for a comprehensive understanding of the topological properties of these two magnetic WSMs and further ARPES and STM measurements.

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

Science.gov (United States)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the

Topological surface Fermi arcs in magnetic Weyl semimetal Co$_3$Sn$_2$S$_2$

OpenAIRE

Xu, Qiunan; Liu, Enke; Shi, Wujun; Muechler, Lukas; Felser, Claudia; Sun, Yan

2017-01-01

Very recently, the half-metallic compound Co$_3$Sn$_2$S$_2$ was predicted to be a magnetic WSM with Weyl points only 60 meV above the Fermi level ($E_F$). Owing to the low charge carrier density and large Berry curvature induced, Co$_3$Sn$_2$S$_2$ possesses both a large anomalous Hall conductivity (AHC) and a large anomalous Hall angle (AHA), which provide strong evidence for the existence of Weyl points in Co$_3$Sn$_2$S$_2$. In this work, we theoretically studied the surface topological feat...

Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

International Nuclear Information System (INIS)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

2015-01-01

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

Characterization of surface antigen protein 1 (SurA1) from Acinetobacter baumannii and its role in virulence and fitness.

Science.gov (United States)

Liu, Dong; Liu, Zeng-Shan; Hu, Pan; Cai, Ling; Fu, Bao-Quan; Li, Yan-Song; Lu, Shi-Ying; Liu, Nan-Nan; Ma, Xiao-Long; Chi, Dan; Chang, Jiang; Shui, Yi-Ming; Li, Zhao-Hui; Ahmad, Waqas; Zhou, Yu; Ren, Hong-Lin

2016-04-15

Acinetobacter baumannii is a Gram-negative bacillus that causes nosocomial infections, such as bacteremia, pneumonia, and meningitis and urinary tract and wound infections. In the present study, the surface antigen protein 1 (SurA1) gene of A. baumannii strain CCGGD201101 was identified, cloned and expressed, and then its roles in fitness and virulence were investigated. Virulence was observed in the human lung cancer cell lines A549 and HEp-2 at one week after treatment with recombinant SurA1. One isogenic SurA1 knock-out strain, GR0015, which was derived from the A. baumannii strain CCGGD201101 isolated from diseased chicks in a previous study, highlighted the effect of SurA1 on fitness and growth. Its growth rate in LB broth and killing activity in human sera were significantly decreased compared with strain CCGGD201101. In the Galleria mellonella insect model, the isogenic SurA1 knock-out strain exhibited a lower survival rate and decreased dissemination. These results suggest that SurA1 plays an important role in the fitness and virulence of A. baumannii. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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

2018-03-14

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

Modelling CO2 emissions from water surface of a boreal hydroelectric reservoir.

Science.gov (United States)

Wang, Weifeng; Roulet, Nigel T; Kim, Youngil; Strachan, Ian B; Del Giorgio, Paul; Prairie, Yves T; Tremblay, Alain

2018-01-15

To quantify CO 2 emissions from water surface of a reservoir that was shaped by flooding the boreal landscape, we developed a daily time-step reservoir biogeochemistry model. We calibrated the model using the measured concentrations of dissolved organic and inorganic carbon (C) in a young boreal hydroelectric reservoir, Eastmain-1 (EM-1), in northern Quebec, Canada. We validated the model against observed CO 2 fluxes from an eddy covariance tower in the middle of EM-1. The model predicted the variability of CO 2 emissions reasonably well compared to the observations (root mean square error: 0.4-1.3gCm -2 day -1 , revised Willmott index: 0.16-0.55). In particular, we demonstrated that the annual reservoir surface effluxes were initially high, steeply declined in the first three years, and then steadily decreased to ~115gCm -2 yr -1 with increasing reservoir age over the estimated "engineering" reservoir lifetime (i.e., 100years). Sensitivity analyses revealed that increasing air temperature stimulated CO 2 emissions by enhancing CO 2 production in the water column and sediment, and extending the duration of open water period over which emissions occur. Increasing the amount of terrestrial organic C flooded can enhance benthic CO 2 fluxes and CO 2 emissions from the reservoir water surface, but the effects were not significant over the simulation period. The model is useful for the understanding of the mechanism of C dynamics in reservoirs and could be used to assist the hydro-power industry and others interested in the role of boreal hydroelectric reservoirs as sources of greenhouse gas emissions. Copyright © 2017 Elsevier B.V. All rights reserved.

High-frequency pressure variations in the vicinity of a surface CO2 flux chamber

Science.gov (United States)

Eugene S. Takle; James R. Brandle; R. A. Schmidt; Rick Garcia; Irina V. Litvina; William J. Massman; Xinhua Zhou; Geoffrey Doyle; Charles W. Rice

2003-01-01

We report measurements of 2Hz pressure fluctuations at and below the soil surface in the vicinity of a surface-based CO2 flux chamber. These measurements were part of a field experiment to examine the possible role of pressure pumping due to atmospheric pressure fluctuations on measurements of surface fluxes of CO2. Under the moderate wind speeds, warm temperatures,...

Surface studies of UFe2 and evaluation of its catalytic properties with a 2H2:CO mixture

International Nuclear Information System (INIS)

Schultz, J.; Naegele, J.; Spirlet, J.C.; Colmenares, C.

1987-01-01

The reactivity of UFe 2 with O 2 , CO and CO 2 were studied using x-ray photoelectron spectroscopy (XPS). Adsorption of O 2 on clean UFe 2 surfaces (Fe/U ≅ 2.0), produced by argon-ion sputtering, leads to the formation of UO 2 and depletion of Fe from the surface layer probed by XPS (Fe/U ≅ 0.8). The oxidation state of Fe in this layer, as determined by XPS (Fe 2p/sub 3/2/ = 710.4 eV), is between Fe +2 and Fe +3 of pure Fe oxides. Exposure of sputtered-clean UFe 2 to CO and CO 2 results in a slight broadening of the U 4f peaks, indicating U oxidation, and some Fe depletion in the analyzed layer (Fe/U ≅ 1.7). The O ls (530.2 and 530.4 eV for CO and CO 2 , respectively) and C ls (282.7 and 282.6 eV for CO and CO 2 , respectively) indicate that dissociative chemisorption to O and C atoms occurs. UFe 2 ground into a fine powder was tested as a catalyst in a differential high-pressure flow reactor with a 2H 2 :CO gas mixture. A significant amount of methanol and hydrocarbons are produced at 577K; while hydrocarbons are the main products (>99%) at 739K. XPS analysis of the used catalyst indicates that U is present as UO/sub 2+x/ and Fe as Fe 2 O 3

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

Science.gov (United States)

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

2017-08-09

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

XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

International Nuclear Information System (INIS)

Wang Xiaolin; Fu Yibei; Xie Renshou

1996-04-01

The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

Surface modification of polyethylene terephthalate using excimer and CO2 laser

International Nuclear Information System (INIS)

Mirzadeh, H.; Dadsetan, M.

2002-01-01

Complete text of publication follows. Attempts have been made to evaluate microstructuring which affects cell behaviour, physical and chemical changes produced by laser irradiation onto the polyethylene terephthalate (PET) surface. The surfaces of PET were irradiated using the CO 2 laser and KrF excimer pulsed laser. The changes in chemical and physical properties of the irradiated PET surface were investigated by attenuated total reflectance infrared spectroscopy (ATR-IR) and contact angle measurements. ATR-IR Spectra showed that the crystallinity in the surface region decreased due to the CO 2 laser and excimer laser irradiation. Scanning electron microscopy observations showed that the morphology of the laser irradiated PET surface changed due to laser irradiation. The results obtained from the cell behaviour studies revealed that changes of physico-chemical properties of the laser treated PET film have significantly changed in comparison with the unmodified PET

Long-term CO2 injection and its impact on near-surface soil microbiology.

Science.gov (United States)

Gwosdz, Simone; West, Julia M; Jones, David; Rakoczy, Jana; Green, Kay; Barlow, Tom; Blöthe, Marco; Smith, Karon; Steven, Michael; Krüger, Martin

2016-12-01

Impacts of long-term CO 2 exposure on environmental processes and microbial populations of near-surface soils are poorly understood. This near-surface long-term CO 2 injection study demonstrated that soil microbiology and geochemistry is influenced more by seasonal parameters than elevated CO 2 Soil samples were taken during a 3-year field experiment including sampling campaigns before, during and after 24 months of continuous CO 2 injection. CO 2 concentrations within CO 2 -injected plots increased up to 23% during the injection period. No CO 2 impacts on geochemistry were detected over time. In addition, CO 2 -exposed samples did not show significant changes in microbial CO 2 and CH 4 turnover rates compared to reference samples. Likewise, no significant CO 2 -induced variations were detected for the abundance of Bacteria, Archaea (16S rDNA) and gene copy numbers of the mcrA gene, Crenarchaeota and amoA gene. The majority (75%-95%) of the bacterial sequences were assigned to five phyla: Firmicutes, Proteobacteria, Actinobacteria, Acidobacteria and Bacteroidetes The majority of the archaeal sequences (85%-100%) were assigned to the thaumarchaeotal cluster I.1b (soil group). Univariate and multivariate statistical as well as principal component analyses showed no significant CO 2 -induced variation. Instead, seasonal impacts especially temperature and precipitation were detected. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Remote sensing algorithm for sea surface CO2 in the Baltic Sea

Science.gov (United States)

Parard, G.; Charantonis, A. A.; Rutgerson, A.

2014-08-01

Studies of coastal seas in Europe have brought forth the high variability in the CO2 system. This high variability, generated by the complex mechanisms driving the CO2 fluxes makes their accurate estimation an arduous task. This is more pronounced in the Baltic Sea, where the mechanisms driving the fluxes have not been as highly detailed as in the open oceans. In adition, the joint availability of in-situ measurements of CO2 and of sea-surface satellite data is limited in the area. In this paper, a combination of two existing methods (Self-Organizing-Maps and Multiple Linear regression) is used to estimate ocean surface pCO2 in the Baltic Sea from remotely sensed surface temperature, chlorophyll, coloured dissolved organic matter, net primary production and mixed layer depth. The outputs of this research have an horizontal resolution of 4 km, and cover the period from 1998 to 2011. The reconstructed pCO2 values over the validation data set have a correlation of 0.93 with the in-situ measurements, and a root mean square error is of 38 μatm. The removal of any of the satellite parameters degraded this reconstruction of the CO2 flux, and we chose therefore to complete any missing data through statistical imputation. The CO2 maps produced by this method also provide a confidence level of the reconstruction at each grid point. The results obtained are encouraging given the sparsity of available data and we expect to be able to produce even more accurate reconstructions in the coming years, in view of the predicted acquisitions of new data.

Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

Science.gov (United States)

Lobo-Lapidus, Rodrigo J; Gates, Bruce C

2010-10-04

Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

A uniform, quality controlled Surface Ocean CO₂ Atlas (SOCAT)

Digital Repository Service at National Institute of Oceanography (India)

Pfeil, B.; Olsen, A; Bakker, D.C.E.; Hankin, S.; Koyuk, H.; Kozyr, A; Malczyk, J.; Manke, A; Metzl, N.; Sabine, C.L.; Akl, J.; Alin, S.R.; Bates, N.; Bellerby, R.G.J.; Borges, A; Boutin, J.; Brown, P.J.; Cai, W.-J.; Chavez, F.P.; Chen, A; Cosca, C.; Fassbender, A.J.; Feely, R.A.; Gonzalez-Davila, M.; Goyet, C.; Hales, B.; Hardman-Mountford, N.; Heinze, C.; Hood, M.; Hoppema, M.; Hunt, C.W.; Hydes, D.; Ishii, M.; Johannessen, T.; Jones, S.D.; Key, R.M.; Kortzinger, A.; Landschutzer, P.; Lauvset, S.K.; Lefevre, N.; Lenton, A.; Lourantou, A.; Merlivat, L.; Midorikawa, T.; Mintrop, L.; Miyazaki, C.; Murata, A.; Nakadate, A.; Nakano, Y.; Nakaoka, S.; Nojiri, Y.; Omar, A.M.; Padin, X.A.; Park, G.-H.; Paterson, K.; Perez, F.F.; Pierrot, D.; Poisson, A.; Rios, A.F.; Santana-Casiano, J.M.; Salisbury, J.; Sarma, V.V.S.S.; et al

by the international marine carbon science community in 2007 with the aim of providing a comprehensive, publicly available, regularly updated, global data set of marine surface CO2, which had been subject to quality control (QC). Many additional CO2 data, not yet made...

CO2 adsorption-assisted CH4 desorption on carbon models of coal surface: A DFT study

Science.gov (United States)

Xu, He; Chu, Wei; Huang, Xia; Sun, Wenjing; Jiang, Chengfa; Liu, Zhongqing

2016-07-01

Injection of CO2 into coal is known to improve the yields of coal-bed methane gas. However, the technology of CO2 injection-enhanced coal-bed methane (CO2-ECBM) recovery is still in its infancy with an unclear mechanism. Density functional theory (DFT) calculations were performed to elucidate the mechanism of CO2 adsorption-assisted CH4 desorption (AAD). To simulate coal surfaces, different six-ring aromatic clusters (2 × 2, 3 × 3, 4 × 4, 5 × 5, 6 × 6, and 7 × 7) were used as simplified graphene (Gr) carbon models. The adsorption and desorption of CH4 and/or CO2 on these carbon models were assessed. The results showed that a six-ring aromatic cluster model (4 × 4) can simulate the coal surface with limited approximation. The adsorption of CO2 onto these carbon models was more stable than that in the case of CH4. Further, the adsorption energies of single CH4 and CO2 in the more stable site were -15.58 and -18.16 kJ/mol, respectively. When two molecules (CO2 and CH4) interact with the surface, CO2 compels CH4 to adsorb onto the less stable site, with a resulting significant decrease in the adsorption energy of CH4 onto the surface of the carbon model with pre-adsorbed CO2. The Mulliken charges and electrostatic potentials of CH4 and CO2 adsorbed onto the surface of the carbon model were compared to determine their respective adsorption activities and changes. At the molecular level, our results showed that the adsorption of the injected CO2 promoted the desorption of CH4, the underlying mechanism of CO2-ECBM.

Near Surface CO2 Triple Oxygen Isotope Composition

Directory of Open Access Journals (Sweden)

Sasadhar Mahata

2016-02-01

Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

CO2 sorption on surface-modified carbonaceous support: Probing the influence of the carbon black microporosity and surface polarity

International Nuclear Information System (INIS)

Gargiulo, Valentina; Alfè, Michela; Ammendola, Paola; Raganati, Federica; Chirone, Riccardo

2016-01-01

Graphical abstract: - Highlights: • CO 2 -sorbent materials preparation by surface modification of CB. • CB functionalization (amino-groups), CB coating (Fe 3 O 4 ), CB impregnation (ionic liquid). • Sorbents bearing basic functionalities exhibit the higher CO 2 sorption capacity. • Microporous supporting material limits the CO 2 accessibility toward the adsorbing material. - Abstract: The use of solid sorbents is a convenient option in post-combustion CO 2 capture strategies. Sorbents selection is a key point because the materials are required to be both low-cost and versatile in typical post-combustion conditions in order to guarantee an economically advantageous overall process. This work compares strategies to tailor the chemico-physical features of carbon black (CB) by surface-modification and/or coating with a CO 2 -sorbent phase. The influence of the CB microporosity, enhanced by chemical/thermal treatments, is also taken into account. Three CB surface modifications are performed and compared: (i) oxidation and functionalization with amino-groups, (ii) coating with iron oxides and (iii) impregnation with an ionic liquid (IL). The CO 2 capture performance is evaluated on the basis of the breakthrough curves measured at atmospheric pressure and room temperature in a lab-scale fixed bed micro-reactor. Most of tested solids adsorb a CO 2 amount significantly higher than a 13X zeolite and DARCO FGD (Norit) activated carbon (up to 4 times more in the best case). The sorbents bearing basic functionalities (amino-groups and IL) exhibit the highest CO 2 sorption capacity. The use of a microporous carbonaceous support limits the accessibility of CO 2 toward the adsorbing phase (IL or FM) lowering the number of accessible binding sites for CO 2 .

A multi-decade record of high-quality fCO2 data in version 3 of the Surface Ocean CO2 Atlas (SOCAT)

Science.gov (United States)

Bakker, Dorothee; Landa, Camilla S.; Pfeil, Benjamin; Metzl, Nicolas; O’Brien, Kevin; Olsen, Are; Smith, Karl; Cosca, Cathy; Harasawa, Sumiko; Nakaoka, Shin-ichiro; Jones, Stephen; Nojiri, Yukihiro; Steinhoff, Tobias; Sweeney, Colm; Schuster, Ute; Takahashi, Taro; Tilbrook, Bronte; Wada, Chisato; Wanninkhof, Rik; Alin, Simone R.; Balestrini, Carlos F.; Barbero, Leticia; Bates, Nicholas; Bianchi, Alejandro A.; Bonou, Frédéric; Boutin, Jacqueline; Bozec, Yann; Burger, Eugene F.; Cai, Wei-Jun; Castle, Robert D.; Chen, Liqi; Chierici, Melissa; Currie, Kim; Evans, Wiley; Featherstone, Charles; Feely, Richard; Fransson, Agneta; Goyet, Catherine; Greenwood, Naomi; Gregor, Luke; Hankin, Steven C.; Hardman-Mountford, Nick J.; Harlay, Jérôme; Hauck, Judith; Hoppema, Mario; Humphreys, Matthew P.; Hunt, Christopher W.; Huss, Betty; Ibánhez, J. Severino P.; Johannessen, Truls; Keeling, Ralph F.; Kitidis, Vassilis; Körtzinger, Arne; Kozyr, Alex; Krasakopoulou, Evangelia; Kuwata, Akira; Landschützer, Peter; Lauvset, Siv K.; Lefèvre, Nathalie; Lo Monaco, Claire; Manke, Ansley; Mathis, Jeremy T.; Merlivat, Liliane; Millero, Frank J.; Monteiro, Pedro M. S.; Munro, David R.; Murata, Akihiko; Newberger, Timothy; Omar, Abdirahman M.; Ono, Tsuneo; Paterson, Kristina; Pearce, David; Pierrot, Denis; Robbins, Lisa L.; Saito, Shu; Salisbury, Joe; Schlitzer, Reiner; Schneider, Bernd; Schweitzer, Roland; Sieger, Rainer; Skjelvan, Ingunn; Sullivan, Kevin F.; Sutherland, Stewart C.; Sutton, Adrienne J.; Tadokoro, Kazuaki; Telszewski, Maciej; Tuma, Matthias; van Heuven, Steven M. A. C.; Vandemark, Douglas; Ward, Brian; Watson, Andrew J.; Xu, Suqing

2016-01-01

The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled f CO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.7 million f CO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.6 million f CO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water f CO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water f CO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) “living data” publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014). 

Low Overpotential and High Current CO2 Reduction with Surface Reconstructed Cu Foam Electrodess

KAUST Repository

Min, Shixiong

2016-06-23

While recent reports have demonstrated that oxide-derived Cu-based electrodes exhibit high selectivity for CO2 reduction at low overpotential, the low catalytic current density (<2 mA/cm2 at -0.45 V vs. RHE) still largely limits its applications for large-scale fuel synthesis. Here we report an extremely high current density for CO2 reduction at low overpotential using a Cu foam electrode prepared by air-oxidation and subsequent electroreduction. Apart from possessing three-dimensional (3D) open frameworks, the resulting Cu foam electrodes prepared at higher temperatures exhibit enhanced electrochemically active surface area and distinct surface structures. In particular, the Cu foam electrode prepared at 500 °C exhibits an extremely high geometric current density of ~9.4 mA/cm2 in CO2-satrurated 0.1 M KHCO3 aqueous solution and achieving ~39% CO and ~23% HCOOH Faradaic efficiencies at -0.45 V vs. RHE. The high activity and significant selectivity enhancement are attributable to the formation of abundant grain-boundary supported active sites and preferable (100) and (111) facets as a result of reconstruction of Cu surface facets. This work demonstrates that the structural integration of Cu foam with open 3D frameworks and the favorable surface structures is a promising strategy to develop an advanced Cu electrocatalyst that can operate at high current density and low overpotential for CO2 reduction.

Geoelectric Monitoring of geological CO2 storage at Ketzin, Germany (CO2SINK project): Downhole and Surface-Downhole measurements

Science.gov (United States)

Kiessling, D.; Schuett, H.; Schoebel, B.; Krueger, K.; Schmidt-Hattenberger, C.; Schilling, F.

2009-04-01

Numerical models of the CO2 storage experiment CO2SINK (CO2 Storage by Injection into a Natural Saline Aquifer at Ketzin), where CO2 is injected into a deep saline aquifer at roughly 650 m depth, yield a CO2 saturation of approximately 50% for large parts of the plume. Archie's equation predicts an increase of the resistivity by a factor of approximately 3 to 4 for the reservoir sandstone, and laboratory tests on Ketzin reservoir samples support this prediction. Modeling results show that tracking the CO2 plume may be doable with crosshole resistivity surveys under these conditions. One injection well and two observation wells were drilled in 2007 to a depth of about 800 m and were completed with "smart" casings, arranged L-shaped with distances of 50 m and 100 m. 45 permanent ring-shaped steel electrodes were attached to the electrically insulated casings of the three Ketzin wells at 590 m to 735 m depth with a spacing of about 10 m. It is to our knowledge the deepest permanent vertical electrical resistivity array (VERA) worldwide. The electrodes are connected to the current power supply and data registration units at the surface through custom-made cables. This deep electrode array allows for the registration of electrical resistivity tomography (ERT) data sets at basically any desired repetition rate and at very low cost, without interrupting the injection operations. The installation of all 45 electrodes succeeded. The electrodes are connected to the electrical cable, and the insulated casing stood undamaged. Even after 2-odd years under underground conditions only 6 electrodes are in a critical state now, caused by corrosion effects. In the framework of the COSMOS project (CO2-Storage, Monitoring and Safety Technology), supported by the German "Geotechnologien" program, the geoelectric monitoring has been performed. The 3D crosshole time-laps measurements are taken using dipole-dipole configurations. The data was inverted using AGI EarthImager 3D to obtain 3D

Climatological Distributions of pH, pCO2, Total CO2, Alkalinity, and CaCO3 Saturation in the Global Surface Ocean (NCEI accession 01645680) (NCEI Accession 0164568)

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — Climatological mean monthly distributions of pH in the total H+ scale, total CO2 concentration (TCO2), and the degree of CaCO3 saturation for the global surface...

An update to the Surface Ocean CO2 Atlas (SOCAT version 2)

Digital Repository Service at National Institute of Oceanography (India)

Bakker, D.C.E.; Hankin, S.; Olsen, A; Pfeil, B.; Smith, K.; Alin, S.R.; Cosca, C.; Hales, B.; Harasawa, S.; Kozyr, A; Nojiri, Y.; OBrien, K.M.; Schuster, U.; Telszewski, M.; Tilbrook, B.; Wada, C.; Akl, J.; Barbero, L.; Bates, N.; Boutin, J.; Cai, W.J.; Castle, R.D.; Chavez, F.; Chen, L.; Chierici, M.; Currie, K.; Evans, W.; Feely, R.A; Fransson, A; Gao, Z.; Hardman-Mountford, N.; Hoppema, M.; Huang, W.J.; Hunt, C.W.; Huss, B.; Ichikawa, T.; Jacobson, A; Johannessen, T.; Jones, E.M.; Jones, S.; Sara, J.; Kitidis, V.; Kortzinger, A.; Lauvset, S.; Lefevre, N.; Manke, A.B.; Mathis, J.; Metzl, N.; Monteiro, P.; Murata, A.; Newberger, T.; Nobuo, T.; Ono, T.; Paterson, K.; Pierrot, D.; Rios, A.F.; Sabine, C.L.; Saito, S.; Salisbury, J.; Sarma, V.V.S.S.; Schlitzer, R.; Sieger, R.; Skjelvan, I.; Steinhoff, T.; Sullivan, K.; Sutherland, S.C.; Suzuki, T.; Sutton, A.; Sweeney, C.; Takahashi, T.; Tjiputra, J.; VanHeuven, S.; Vandemark, D.; Vlahos, P.; Wallace, D.W.R.; Wanninkhof, R.; Watson, A.J.

of SOCAT is an update of the previous release (version 1) with more data (increased from 6.3 million to 10.1 million surface water fCO₂ values) and extended data coverage (from 1968–2007 to 1968–2011). The quality control criteria, while...

Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

2015-10-15

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

Strong and weak adsorption of CO{sub 2} on PuO{sub 2} (1 1 0) surfaces from first principles calculations

Energy Technology Data Exchange (ETDEWEB)

Yu, H.L. [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Department of Engineering Physics, Tsinghua University, Beijing 100084 (China); Deng, X.D. [Department of Engineering Physics, Tsinghua University, Beijing 100084 (China); Li, G.; Lai, X.C. [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Meng, D.Q., E-mail: yuhuilong2002@126.com [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China)

2014-10-15

Highlights: • The CO{sub 2} adsorption on PuO{sub 2} (1 1 0) surface was studied by GGA + U. • Both weak and strong adsorptions exist between CO{sub 2} and the PuO{sub 2} (1 1 0) surface. • Electrostatic interactions were involved in the weak interactions. • Covalent bonding was developed in the strong adsorptions. - Abstract: The CO{sub 2} adsorption on plutonium dioxide (PuO{sub 2}) (1 1 0) surface was studied using projector-augmented wave (PAW) method based on density-functional theory corrected for onsite Coulombic interactions (GGA + U). It is found that CO{sub 2} has several different adsorption features on PuO{sub 2} (1 1 0) surface. Both weak and strong adsorptions exist between CO{sub 2} and the PuO{sub 2} (1 1 0) surface. Further investigation of partial density of states (PDOS) and charge density difference on two typical absorption sites reveal that electrostatic interactions were involved in the weak interactions, while covalent bonding was developed in the strong adsorptions.

Parameterization of atmosphere-surface exchange of CO₂ over sea ice

DEFF Research Database (Denmark)

Sørensen, L. L.; Jensen, B.; Glud, Ronnie N.

2014-01-01

are discussed. We found the flux to be small during the late winter with fluxes in both directions. Not surprisingly we find that the resistance across the surface controls the fluxes and detailed knowledge of the brine volume and carbon chemistry within the brines as well as knowledge of snow cover and carbon...... chemistry in the ice are essential to estimate the partial pressure of pCO2 and CO2 flux. Further investigations of surface structure and snow cover and driving parameters such as heat flux, radiation, ice temperature and brine processes are required to adequately parameterize the surface resistance....

Subsurface oxide plays a critical role in CO_2 activation by Cu(111) surfaces to form chemisorbed CO_2 , the first step in reduction of CO_2

OpenAIRE

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A.; Yano, Junko; Crumlin, Ethan J.

2017-01-01

A national priority is to convert CO_2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO_2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide s...

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

OpenAIRE

Favaro, M; Xiao, H; Cheng, T; Goddard, WA; Crumlin, EJ

2017-01-01

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide str...

Inferring CO2 Fluxes from OCO-2 for Assimilation into Land Surface Models to Calculate Net Ecosystem Exchange

Science.gov (United States)

Prouty, R.; Radov, A.; Halem, M.; Nearing, G. S.

2016-12-01

Investigations of mid to high latitude atmospheric CO2 show a growing seasonal amplitude. Land surface models poorly predict net ecosystem exchange (NEE) and are unable to substantiate these sporadic observations. An investigation of how the biosphere has reacted to changes in atmospheric CO2 is essential to our understanding of potential climate-vegetation feedbacks. A global, seasonal investigation of CO2-flux is then necessary in order to assimilate into land surface models for improving the prediction of annual NEE. The Atmospheric Radiation Measurement program (ARM) of DOE collects CO2-flux measurements (in addition to CO2 concentration and various other meteorological quantities) at several towers located around the globe at half hour temporal frequencies. CO2-fluxes are calculated via the eddy covariance technique, which utilizes CO2-densities and wind velocities to calculate CO2-fluxes. The global coverage of CO2 concentrations as provided by the Orbiting Carbon Observatory (OCO-2) provide satellite-derived CO2 concentrations all over the globe. A framework relating the satellite-inferred CO2 concentrations collocated with the ground-based ARM as well as Ameriflux stations would enable calculations of CO2-fluxes far from the station sites around the entire globe. Regression techniques utilizing deep-learning neural networks may provide such a framework. Additionally, meteorological reanalysis allows for the replacement of the ARM multivariable meteorological variables needed to infer the CO2-fluxes. We present the results of inferring CO2-fluxes from OCO-2 CO2 concentrations for a two year period, Sept. 2014- Sept. 2016 at the ARM station located near Oklahoma City. A feed-forward neural network (FFNN) is used to infer relationships between the following data sets: F([ARM CO2-density], [ARM Meteorological Data]) = [ARM CO2-Flux] F([OCO-2 CO2-density],[ARM Meteorological Data]) = [ARM CO2-Flux] F([ARM CO2-density],[Meteorological Reanalysis]) = [ARM CO2-Flux

Investigation de l'anisotropie du gap supraconducteur dans les composes Ba(Fe(1-x)Co(x))2As2, Ba(1-x)K(x)Fe2As2, LiFeAs et Fe1-deltaTe(1-x)Se(x)

Science.gov (United States)

Reid, Jean-Philippe

ommaire La structure du gap supraconducteur et sa modulation sont intimement liees au potentiel d'interaction responsable de l'appariement des electrons d'un supraconducteur. Ainsi, l'etude de la structure du gap-SC et de sa modulation permettent de faire la lumiere sur la nature du mecanisme d'appariement des electrons. A cet egard, les resultats experimentaux des supraconducteurs a base de fer ne cadrent pas dans un seul ensemble, ce qui est en opposition au gap-SC universel des cuprates. Dans ce qui suit, nous presenterons une etude systematique du gap-SC pour plusieurs pnictides. En effet, en utilisant la conductivite thermique, une sonde directionnelle du gap-SC, nous avons ete en mesure de reveler la structure du gap-SC pour les composes suivants : Ba1-xKxFe 2As2, Ba(Fe1-xCo x)2As2, LiFeAs et Fe1-deltaTe 1-xSex. L'etude de ces quatre composes, de trois differentes familles structurales, a pu etablir un tableau partiel mais tres exhaustif de la structure du gap-SC de pnictides. En effet, tel qu'illustre dans cette these, ces quatre composes ne possedent aucun noeud dans leur structure du gap-SC a dopage optimal. Toutefois, a une concentration differente de celle optimale pour les composes K-Ba122 et Co-Ba122, des noeuds apparaissent sur la surface de Fermi, aux extremites 'du dome supraconducteur. Ceci suggere fortement que, pour ces composes, la presence de noeuds sur la surface de Fermi est nuisible a la phase supraconductrice. Mots-cles: Supraconducteurs a base de fer, Pnictides, Structure du gap supraconducteur, Conductivite thermique

A microporous MOF with a polar pore surface exhibiting excellent selective adsorption of CO2 from CO2-N2 and CO2-CH4 gas mixtures with high CO2 loading.

Science.gov (United States)

Pal, Arun; Chand, Santanu; Elahi, Syed Meheboob; Das, Madhab C

2017-11-14

A microporous MOF {[Zn(SDB)(L) 0.5 ]·S} n (IITKGP-5) with a polar pore surface has been constructed by the combination of a V-shaped -SO 2 functionalized organic linker (H 2 SDB = 4,4'-sulfonyldibenzoic acid) with an N-rich spacer (L = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene), forming a network with sql(2,6L1) topology. IITKGP-5 is characterized by TGA, PXRD and single crystal X-ray diffraction. The framework exhibits lozenge-shaped channels of an approximate size of 4.2 × 5.6 Å 2 along the crystallographic b axis with a potential solvent accessible volume of 26%. The activated IITKGP-5a revealed a CO 2 uptake capacity of 56.4 and 49 cm 3 g -1 at 273 K/1 atm and 295 K/1 atm, respectively. On the contrary, it takes up a much smaller amount of CH 4 (17 cm 3 g -1 at 273 K and 13.6 cm 3 g -1 at 295 K) and N 2 (5.5 cm 3 g -1 at 273 K; 4 cm 3 g -1 at 295 K) under 1 atm pressure exhibiting its potential for a highly selective adsorption of CO 2 from flue gas as well as a landfill gas mixture. Based on the ideal adsorbed solution theory (IAST), a CO 2 /N 2 selectivity of 435.5 and a CO 2 /CH 4 selectivity of 151.6 have been realized at 273 K/100 kPa. The values at 295 K are 147.8 for CO 2 /N 2 and 23.8 for CO 2 /CH 4 gas mixtures under 100 kPa. In addition, this MOF nearly approaches the target values proposed for PSA and TSA processes for practical utility exhibiting its prospect for flue gas separation with a CO 2 loading capacity of 2.04 mmol g -1 .

CO{sub 2} sorption on surface-modified carbonaceous support: Probing the influence of the carbon black microporosity and surface polarity

Energy Technology Data Exchange (ETDEWEB)

Gargiulo, Valentina [Istituto di Ricerche sulla Combustione (IRC)-CNR, Piazzale V. Tecchio 80, 80125 Napoli (Italy); Alfè, Michela, E-mail: alfe@irc.cnr.it [Istituto di Ricerche sulla Combustione (IRC)-CNR, Piazzale V. Tecchio 80, 80125 Napoli (Italy); Ammendola, Paola [Istituto di Ricerche sulla Combustione (IRC)-CNR, Piazzale V. Tecchio 80, 80125 Napoli (Italy); Raganati, Federica [Università degli Studi di Napoli “Federico II”, Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Piazzale V. Tecchio 80, 80125 Napoli (Italy); Chirone, Riccardo [Istituto di Ricerche sulla Combustione (IRC)-CNR, Piazzale V. Tecchio 80, 80125 Napoli (Italy)

2016-01-01

Graphical abstract: - Highlights: • CO{sub 2}-sorbent materials preparation by surface modification of CB. • CB functionalization (amino-groups), CB coating (Fe{sub 3}O{sub 4}), CB impregnation (ionic liquid). • Sorbents bearing basic functionalities exhibit the higher CO{sub 2} sorption capacity. • Microporous supporting material limits the CO{sub 2} accessibility toward the adsorbing material. - Abstract: The use of solid sorbents is a convenient option in post-combustion CO{sub 2} capture strategies. Sorbents selection is a key point because the materials are required to be both low-cost and versatile in typical post-combustion conditions in order to guarantee an economically advantageous overall process. This work compares strategies to tailor the chemico-physical features of carbon black (CB) by surface-modification and/or coating with a CO{sub 2}-sorbent phase. The influence of the CB microporosity, enhanced by chemical/thermal treatments, is also taken into account. Three CB surface modifications are performed and compared: (i) oxidation and functionalization with amino-groups, (ii) coating with iron oxides and (iii) impregnation with an ionic liquid (IL). The CO{sub 2} capture performance is evaluated on the basis of the breakthrough curves measured at atmospheric pressure and room temperature in a lab-scale fixed bed micro-reactor. Most of tested solids adsorb a CO{sub 2} amount significantly higher than a 13X zeolite and DARCO FGD (Norit) activated carbon (up to 4 times more in the best case). The sorbents bearing basic functionalities (amino-groups and IL) exhibit the highest CO{sub 2} sorption capacity. The use of a microporous carbonaceous support limits the accessibility of CO{sub 2} toward the adsorbing phase (IL or FM) lowering the number of accessible binding sites for CO{sub 2}.

Mass transfer of CO2 to groundwaters from a near-surface waste disposal site

International Nuclear Information System (INIS)

Caron, F.; Wilkinson, S.R.; Manni, G.; Torok, J.

1995-01-01

Gaseous 14 CO 2 originating from buried low-level radioactive wastes (LLRW) in a near-surface disposal site can be released to the environment via two major paths: gas-phase diffusion through soils to the atmosphere, and dissolution in groundwater, followed by aqueous migration. Aqueous migration would give the highest dose to an individual, especially if C-14 was converted to an organic form and ingested. Gaseous diffusion would give a lower dose, largely because of atmospheric dispersion and dilution. The objective of this study was to develop the capability to estimate which of the two paths will likely be dominant for typical near-surface disposal facilities. The main missing parameter for making this estimate was a mass-transfer coefficient (K L ) of 14 CO 2 to groundwaters, which was determined experimentally using a large sand box. The K L thus determined was approximately 10 to 20 times smaller than for an open liquid surface. This suggests that there is a potential resistance to mass transfer, probably caused by the capillary fringe. The value obtained was incorporated into a simple model of CO 2 transport around a typical near-surface disposal site. The model suggests that CO 2 transport via both gaseous release and aqueous migration paths are of similar magnitude for a repository located ∼2 m above the water table. (author). 11 refs., 2 tabs., 2 figs

Water Contact Angle Dependence with Hydroxyl Functional Groups on Silica Surfaces under CO2 Sequestration Conditions.

Science.gov (United States)

Chen, Cong; Zhang, Ning; Li, Weizhong; Song, Yongchen

2015-12-15

Functional groups on silica surfaces under CO2 sequestration conditions are complex due to reactions among supercritical CO2, brine and silica. Molecular dynamics simulations have been performed to investigate the effects of hydroxyl functional groups on wettability. It has been found that wettability shows a strong dependence on functional groups on silica surfaces: silanol number density, space distribution, and deprotonation/protonation degree. For neutral silica surfaces with crystalline structure (Q(3), Q(3)/Q(4), Q(4)), as silanol number density decreases, contact angle increases from 33.5° to 146.7° at 10.5 MPa and 318 K. When Q(3) surface changes to an amorphous structure, water contact angle increases 20°. Water contact angle decreases about 12° when 9% of silanol groups on Q(3) surface are deprotonated. When the deprotonation degree increases to 50%, water contact angle decreases to 0. The dependence of wettability on silica surface functional groups was used to analyze contact angle measurement ambiguity in literature. The composition of silica surfaces is complicated under CO2 sequestration conditions, the results found in this study may help to better understand wettability of CO2/brine/silica system.

A first principles study of the adsorption and dissociation of CO2 on the δ-Pu (111) surface

International Nuclear Information System (INIS)

Atta-Fynn, R.; Raya, A.K.

2009-01-01

A complete understanding of the nature of the 5f electrons has been and continues to be a major scientific problem in condensed matter physics. Bulk and surface electronic structure studies of the actinides as also atomic and molecular adsorptions on the actinide surfaces provide a path towards this understanding. In this work, ab initio calculations within the framework of density functional theory have been used to study the adsorption of molecular CO 2 and the corresponding partially dissociated (CO+O) and completely dissociated (C+O+O) products on the δ-Pu (111) surface. The completely dissociated C+O+O configurations exhibit the strongest binding with the surface (7.92 eV), followed by partially dissociated products CO+O (5.08 eV), with molecular CO 2 adsorption having the lowest binding energies (2.35 eV). For all initial vertically upright orientations, the CO 2 molecule physi-sorbs or do not bind to the surface and the geometry and orientation do not change. For all initial flat lying orientations chemisorption occurs, with the final state corresponding to a bent CO 2 molecule with bond angles of 117-130 degrees and the elongation of the CO bond. For CO+O co-adsorption, the stable configurations corresponded to CO dipole moment orientations of 100-172 degrees with respect to the surface normal and the elongation of the CO bond. The most stable chemisorption cases correspond to anomalously large rumpling of the top Pu layer. The interactions of the CO 2 and CO with the Pu surface have been analyzed using the energy density of states and difference charge density distributions. The nature and the behavior of the 5f electrons have also been discussed in detail in the context of this study. (authors)

Interaction of photoactive cis(CO)-trans(I)-Ru-(4,4‧-dicarboxylate-2,2‧-bipyridine)(CO)2I2 with anatase (1 0 1) surface

Science.gov (United States)

Haukka, Matti; Hirva, Pipsa

2002-06-01

The coordination of cis(CO)-trans(I)-Ru(4,4‧-dicarboxylate-2,2‧-bipyridine)(CO)2I2 on an anatase (1 0 1) surface was investigated using a computational density functional method. The adsorbate is able to interact with the anatase surface by one or two carboxylate substituents of the bipyridine ligand. Three of the studied coordination modes involved a single carboxylate as the binding group, including monodentate (1M), bidentate chelating (1BC) and bidentate bridging (1BB) modes. The possibility of monodentate binding via both carboxylate groups in (2M) was also studied. The results showed that the multidentate binding is clearly preferred over monodentate coordination. The stability of the modes increased in the order 1M, 1BC, 1BB and 2M. The flexibility of the bipyridine ligand was found to be the key factor in the binding via two carboxylate groups.

Correlation between Surface Roughness Characteristics in CO2 Laser Cutting of Mild Steel

Directory of Open Access Journals (Sweden)

M. Radovanović

2012-12-01

Full Text Available CO2 laser oxygen cutting of mild steel is widely used industrial application. Cut surface quality is a very important characteristic of laser cutting that ensures an advantage over other contour cutting processes. In this paper mathematical models for estimating characteristics of surface quality such as average surface roughness and ten-point mean roughness in CO2 laser cutting of mild steel based on laser cutting parameters were developed. Empirical models were developed using artificial neural networks and experimental data collected. Taguchi’s orthogonal array was implemented for experimental plan. From the analysis of the developed mathematical models it was observed that functional dependence between laser cutting parameters, their interactions and surface roughness characteristics is complex and non-linear. It was also observed that there exist region of minimal average surface roughness to ten-point mean roughness ratio. The relationship between average surface roughness and ten-point mean roughness was found to be nonlinear and can be expressed with a second degree polynomial.

Global CO2 fluxes estimated from GOSAT retrievals of total column CO2

Directory of Open Access Journals (Sweden)

S. Basu

2013-09-01

Full Text Available We present one of the first estimates of the global distribution of CO2 surface fluxes using total column CO2 measurements retrieved by the SRON-KIT RemoTeC algorithm from the Greenhouse gases Observing SATellite (GOSAT. We derive optimized fluxes from June 2009 to December 2010. We estimate fluxes from surface CO2 measurements to use as baselines for comparing GOSAT data-derived fluxes. Assimilating only GOSAT data, we can reproduce the observed CO2 time series at surface and TCCON sites in the tropics and the northern extra-tropics. In contrast, in the southern extra-tropics GOSAT XCO2 leads to enhanced seasonal cycle amplitudes compared to independent measurements, and we identify it as the result of a land–sea bias in our GOSAT XCO2 retrievals. A bias correction in the form of a global offset between GOSAT land and sea pixels in a joint inversion of satellite and surface measurements of CO2 yields plausible global flux estimates which are more tightly constrained than in an inversion using surface CO2 data alone. We show that assimilating the bias-corrected GOSAT data on top of surface CO2 data (a reduces the estimated global land sink of CO2, and (b shifts the terrestrial net uptake of carbon from the tropics to the extra-tropics. It is concluded that while GOSAT total column CO2 provide useful constraints for source–sink inversions, small spatiotemporal biases – beyond what can be detected using current validation techniques – have serious consequences for optimized fluxes, even aggregated over continental scales.

Facile synthesis of surface N-doped Bi_2O_2CO_3: Origin of visible light photocatalytic activity and in situ DRIFTS studies

International Nuclear Information System (INIS)

Zhou, Ying; Zhao, Ziyan; Wang, Fang; Cao, Kun; Doronkin, Dmitry E.; Dong, Fan; Grunwaldt, Jan-Dierk

2016-01-01

Graphical abstract: Surfactant (CTAB) can induce nitrogen interstitially doping in the Bi_2O_2CO_3 surface, leading to the formation of localized states from N−O bond, which probably account for the origin of the visible light activity. Moreover, the photocatalytic NO oxidation processes over Bi_2O_2CO_3 were successfully monitored for the first time by in situ DRIFTS. - Highlights: • Interstitially doping N in the Bi_2O_2CO_3 surface was achieved at room temperature. • N-doped Bi_2O_2CO_3 exhibited significantly enhanced visible light photocatalytic activity compared to the pristine Bi_2O_2CO_3. • The formation of localized states from N−O bond could account for the visible light activity of Bi_2O_2CO_3. • The photocatalytic NO oxidation process was monitored by in situ DRIFTS. - Abstract: Bi_2O_2CO_3 nanosheets with exposed {001} facets were prepared by a facile room temperature chemical method. Due to the high oxygen atom density in {001} facets of Bi_2O_2CO_3, the addition of cetyltrimethylammonium bromide (CTAB) does not only influence the growth of crystalline Bi_2O_2CO_3, but also modifies the surface properties of Bi_2O_2CO_3 through the interaction between CTAB and Bi_2O_2CO_3. Nitrogen from CTAB as dopant interstitially incorporates in the Bi_2O_2CO_3 surface evidenced by both experimental and theoretical investigations. Hence, the formation of localized states from N−O bond improves the visible light absorption and charge separation efficiency, which leads to an enhancement of visible light photocatalytic activity toward to the degradation of Rhodamine B (RhB) and oxidation of NO. In addition, the photocatalytic NO oxidation over Bi_2O_2CO_3 nanosheets was successfully monitored for the first time using in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS). Both bidentate and monodentate nitrates were identified on the surface of catalysts during the photocatalytic reaction process. The application of this strategy to

Effect of plasma-induced surface charging on catalytic processes: application to CO2 activation

Science.gov (United States)

Bal, Kristof M.; Huygh, Stijn; Bogaerts, Annemie; Neyts, Erik C.

2018-02-01

Understanding the nature and effect of the multitude of plasma-surface interactions in plasma catalysis is a crucial requirement for further process development and improvement. A particularly intriguing and rather unique property of a plasma-catalytic setup is the ability of the plasma to modify the electronic structure, and hence chemical properties, of the catalyst through charging, i.e. the absorption of excess electrons. In this work, we develop a quantum chemical model based on density functional theory to study excess negative surface charges in a heterogeneous catalyst exposed to a plasma. This method is specifically applied to investigate plasma-catalytic CO2 activation on supported M/Al2O3 (M = Ti, Ni, Cu) single atom catalysts. We find that (1) the presence of a negative surface charge dramatically improves the reductive power of the catalyst, strongly promoting the splitting of CO2 to CO and oxygen, and (2) the relative activity of the investigated transition metals is also changed upon charging, suggesting that controlled surface charging is a powerful additional parameter to tune catalyst activity and selectivity. These results strongly point to plasma-induced surface charging of the catalyst as an important factor contributing to the plasma-catalyst synergistic effects frequently reported for plasma catalysis.

Surface-downhole and crosshole geoelectrics for monitoring of brine injection at the Ketzin CO2 storage site

Science.gov (United States)

Rippe, Dennis; Bergmann, Peter; Labitzke, Tim; Wagner, Florian; Schmidt-Hattenberger, Cornelia

2016-04-01

The Ketzin pilot site in Germany is the longest operating on-shore CO2 storage site in Europe. From June 2008 till August 2013, a total of ˜67,000 tonnes of CO2 were safely stored in a saline aquifer at depths of 630 m to 650 m. The storage site has now entered the abandonment phase, and continuation of the multi-disciplinary monitoring as part of the national project "CO2 post-injection monitoring and post-closure phase at the Ketzin pilot site" (COMPLETE) provides the unique chance to participate in the conclusion of the complete life cycle of a CO2 storage site. As part of the continuous evaluation of the functionality and integrity of the CO2 storage in Ketzin, from October 12, 2015 till January 6, 2015 a total of ˜2,900 tonnes of brine were successfully injected into the CO2 reservoir, hereby simulating in time-lapse the natural backflow of brine and the associated displacement of CO2. The main objectives of this brine injection experiment include investigation of how much of the CO2 in the pore space can be displaced by brine and if this displacement of CO2 during the brine injection differs from the displacement of formation fluid during the initial CO2 injection. Geophysical monitoring of the brine injection included continuous geoelectric measurements accompanied by monitoring of pressure and temperature conditions in the injection well and two adjacent observation wells. During the previous CO2 injection, the geoelectrical monitoring concept at the Ketzin pilot site consisted of permanent crosshole measurements and non-permanent large-scale surveys (Kiessling et al., 2010). Time-lapse geoelectrical tomographies derived from the weekly crosshole data at near-wellbore scale complemented by six surface-downhole surveys at a scale of 1.5 km showed a noticeable resistivity signature within the target storage zone, which was attributed to the CO2 plume (Schmidt-Hattenberger et al., 2011) and interpreted in terms of relative CO2 and brine saturations (Bergmann

Sum frequency generation of CO on (III) and polycrystalline platinum electrode surfaces: Evidence for SFG invisible surface CO

Energy Technology Data Exchange (ETDEWEB)

Baldelli, S.; Markovic, N.; Ross, P.; Shen, Y.R.; Somorjai, G.

1999-10-21

The vibrational spectroscopy sum frequency generation (SFG) is used to investigate the adsorption of carbon monoxide on the single crystal (111) and polycrystalline platinum surfaces. By varying the frequency and polarization of the light beams, different surface species of CO species are probed. SFG signal intensities for different polarization indicate that adsorbed CO polarizability is significantly perturbed from the gas-phase molecule. The SFG signal of CO disappears well below the main oxidation potential of CO to CO{sub 2}. The disappearance of the CO signal is interpreted as a transformation in the CO layer to a state which is invisible to SFG. The invisible state is suggested to be CO with the bond axis nearly parallel to the platinum surface.

Eddy covariance observations of surface leakage during shallow subsurface CO2 releases

Science.gov (United States)

Lewicki, Jennifer L.; Hilley, George E.; Fischer, Marc L.; Pan, Lehua; Oldenburg, Curtis M.; Dobeck, Laura; Spangler, Lee

2009-06-01

We tested the ability of eddy covariance (EC) to detect, locate, and quantify surface CO2 flux leakage signals within a background ecosystem. For 10 days starting on 9 July 2007, and for 7 days starting on 3 August 2007, 0.1 (Release 1) and 0.3 (Release 2) t CO2 d-1, respectively, were released from a horizontal well ˜100 m in length and ˜2.5 m in depth located in an agricultural field in Bozeman, Montana. An EC station measured net CO2 flux (Fc) from 8 June 2006 to 4 September 2006 (mean and standard deviation = -12.4 and 28.1 g m-2 d-1, respectively) and from 28 May 2007 to 4 September 2007 (mean and standard deviation = -12.0 and 28.1 g m-2 d-1, respectively). The Release 2 leakage signal was visible in the Fc time series, whereas the Release 1 signal was difficult to detect within variability of ecosystem fluxes. To improve detection ability, we calculated residual fluxes (Fcr) by subtracting fluxes corresponding to a model for net ecosystem exchange from Fc. Fcr had reduced variability and lacked the negative bias seen in corresponding Fc distributions. Plotting the upper 90th percentile Fcr versus time enhanced the Release 2 leakage signal. However, values measured during Release 1 fell within the variability assumed to be related to unmodeled natural processes. Fcr measurements and corresponding footprint functions were inverted using a least squares approach to infer the spatial distribution of surface CO2 fluxes during Release 2. When combined with flux source area evaluation, inversion results roughly located the CO2 leak, while resolution was insufficient to quantify leakage rate.

Surface Pressure Dependencies in the GEOS-Chem-Adjoint System and the Impact of the GEOS-5 Surface Pressure on CO2 Model Forecast

Science.gov (United States)

Lee, Meemong; Weidner, Richard

2016-01-01

In the GEOS-Chem Adjoint (GCA) system, the total (wet) surface pressure of the GEOS meteorology is employed as dry surface pressure, ignoring the presence of water vapor. The Jet Propulsion Laboratory (JPL) Carbon Monitoring System (CMS) research team has been evaluating the impact of the above discrepancy on the CO2 model forecast and the CO2 flux inversion. The JPL CMS research utilizes a multi-mission assimilation framework developed by the Multi-Mission Observation Operator (M2O2) research team at JPL extending the GCA system. The GCA-M2O2 framework facilitates mission-generic 3D and 4D-variational assimilations streamlining the interfaces to the satellite data products and prior emission inventories. The GCA-M2O2 framework currently integrates the GCA system version 35h and provides a dry surface pressure setup to allow the CO2 model forecast to be performed with the GEOS-5 surface pressure directly or after converting it to dry surface pressure.

Observational determination of surface radiative forcing by CO2 from 2000 to 2010.

Science.gov (United States)

Feldman, D R; Collins, W D; Gero, P J; Torn, M S; Mlawer, E J; Shippert, T R

2015-03-19

The climatic impact of CO2 and other greenhouse gases is usually quantified in terms of radiative forcing, calculated as the difference between estimates of the Earth's radiation field from pre-industrial and present-day concentrations of these gases. Radiative transfer models calculate that the increase in CO2 since 1750 corresponds to a global annual-mean radiative forcing at the tropopause of 1.82 ± 0.19 W m(-2) (ref. 2). However, despite widespread scientific discussion and modelling of the climate impacts of well-mixed greenhouse gases, there is little direct observational evidence of the radiative impact of increasing atmospheric CO2. Here we present observationally based evidence of clear-sky CO2 surface radiative forcing that is directly attributable to the increase, between 2000 and 2010, of 22 parts per million atmospheric CO2. The time series of this forcing at the two locations-the Southern Great Plains and the North Slope of Alaska-are derived from Atmospheric Emitted Radiance Interferometer spectra together with ancillary measurements and thoroughly corroborated radiative transfer calculations. The time series both show statistically significant trends of 0.2 W m(-2) per decade (with respective uncertainties of ±0.06 W m(-2) per decade and ±0.07 W m(-2) per decade) and have seasonal ranges of 0.1-0.2 W m(-2). This is approximately ten per cent of the trend in downwelling longwave radiation. These results confirm theoretical predictions of the atmospheric greenhouse effect due to anthropogenic emissions, and provide empirical evidence of how rising CO2 levels, mediated by temporal variations due to photosynthesis and respiration, are affecting the surface energy balance.

Impact of CO/sub 2/ on cooling of snow and water surfaces

Energy Technology Data Exchange (ETDEWEB)

Choudhury, B [Computer Sciences Corp., Silver Spring, MD; Kukla, G

1979-08-23

The levels of CO/sub 2/ in the atmosphere are being increased by the burning of fossil fuels and reduction of biomass. It has been calculated that the increase in CO/sub 2/ levels should lead to global warming because of increased absorption by the atmosphere of terrestrial longwave radiation in the far IR (> 5 ..mu..m). From model computations, CO/sub 2/ is expected to produce the largest climatic effect in high latitudes by reducing the size of ice and snow fields. We present here computations of spectral radiative transfer and scattering within a snow pack and water. The results suggest that CO/sub 2/ significantly reduces the shortwave energy absorbed by the surface of snow and water. The energy deficit, when not compensated by downward atmospheric radiation, may delay the recrystallisation of snow and dissipation of packice and result in a cooling rather than a warming effect.

Oxidation Behavior of Surface-modified Stainless Steel 316LN in Supercritical-CO{sub 2} Environment

Energy Technology Data Exchange (ETDEWEB)

Kim, Sung Hwan; Heo, Jin Woo; Kim, Hyunm Yung; Jang, Chang Heui [KAIST, Daejeon (Korea, Republic of)

2016-05-15

Compared to other working fluids such as helium or nitrogen, S-CO{sub 2} offers a higher efficiency at operating temperatures of advanced reactors above 550 .deg. C. Moreover, the S-CO{sub 2} cycle is expected to have a significantly smaller footprint compared to other power conversion cycles, resulting in a broader range of applications with lower capital costs. Currently, stainless steel 316 is considered as the candidate structural material for the SFR. In comparison, it is well known that alumina (Al{sub 2}O{sub 3}) have superior oxidation and carburization resistance specifically at higher temperatures where α-Al{sub 2}O{sub 3} may form. Thus, various surface modification techniques have been applied to mostly Ni-base alloys so that a protective and continuous Al-rich oxide layer forms on the surface, conferring superior oxidation and carburization resistance. In this study, SS 316LN was deposited with Al via physical vapor deposition (PVD) method followed by heat treatment processes to develop an Al-rich layer at the surface. The specimens are to be exposed to high temperature S-CO{sub 2} environment to evaluate the oxidation and carburization resistance. Stainless steel 316LN was surface-modified to develop an Al-rich layer for improvement of oxidation behavior in S-CO{sub 2} environment. As the test temperature of 600 .deg. C is not sufficiently high for the formation of protective α-Al{sub 2}O{sub 3} formation, pre-oxidation of surface modified SS 316LN was conducted.

Remote sensing the sea surface CO2 of the Baltic Sea using the SOMLO methodology

Science.gov (United States)

Parard, G.; Charantonis, A. A.; Rutgerson, A.

2015-06-01

Studies of coastal seas in Europe have noted the high variability of the CO2 system. This high variability, generated by the complex mechanisms driving the CO2 fluxes, complicates the accurate estimation of these mechanisms. This is particularly pronounced in the Baltic Sea, where the mechanisms driving the fluxes have not been characterized in as much detail as in the open oceans. In addition, the joint availability of in situ measurements of CO2 and of sea-surface satellite data is limited in the area. In this paper, we used the SOMLO (self-organizing multiple linear output; Sasse et al., 2013) methodology, which combines two existing methods (i.e. self-organizing maps and multiple linear regression) to estimate the ocean surface partial pressure of CO2 (pCO2) in the Baltic Sea from the remotely sensed sea surface temperature, chlorophyll, coloured dissolved organic matter, net primary production, and mixed-layer depth. The outputs of this research have a horizontal resolution of 4 km and cover the 1998-2011 period. These outputs give a monthly map of the Baltic Sea at a very fine spatial resolution. The reconstructed pCO2 values over the validation data set have a correlation of 0.93 with the in situ measurements and a root mean square error of 36 μatm. Removing any of the satellite parameters degraded this reconstructed CO2 flux, so we chose to supply any missing data using statistical imputation. The pCO2 maps produced using this method also provide a confidence level of the reconstruction at each grid point. The results obtained are encouraging given the sparsity of available data, and we expect to be able to produce even more accurate reconstructions in coming years, given the predicted acquisition of new data.

Generation of Cu–In alloy surfaces from CuInO2 as selective catalytic sites for CO2 electroreduction

KAUST Repository

Jedidi, Abdesslem

2015-08-11

The lack of availability of efficient, selective and stable electrocatalysts is a major hindrance for scalable CO2 reduction processes. Herein, we report the generation of Cu–In alloy surfaces for electrochemical reduction of CO2 from mixed metal oxides of CuInO2 as the starting material. The material successfully generates selective active sites to form CO from CO2 electroreduction at mild overpotentials. Density functional theory (DFT) indicates that the site occupation of the inert In occurs more on the specific sites of Cu. In addition, while In atoms do not preferentially adsorb H or CO, Cu atoms, which neighbor the In atoms, alters the preference of their adsorption. This preference for site occupation and altered adsorption may account for the improved selectivity over that observed for Cu metal. This study demonstrates an example of a scalable synthesis method of bimetallic surfaces utilized with the mixed oxide precursor having the diversity of metal choice, which may drastically alter the electrocatalytic performance, as presented herein.

Generation of Cu–In alloy surfaces from CuInO2 as selective catalytic sites for CO2 electroreduction

KAUST Repository

Jedidi, Abdesslem; Rasul, Shahid; Masih, Dilshad; Cavallo, Luigi; Takanabe, Kazuhiro

2015-01-01

The lack of availability of efficient, selective and stable electrocatalysts is a major hindrance for scalable CO2 reduction processes. Herein, we report the generation of Cu–In alloy surfaces for electrochemical reduction of CO2 from mixed metal oxides of CuInO2 as the starting material. The material successfully generates selective active sites to form CO from CO2 electroreduction at mild overpotentials. Density functional theory (DFT) indicates that the site occupation of the inert In occurs more on the specific sites of Cu. In addition, while In atoms do not preferentially adsorb H or CO, Cu atoms, which neighbor the In atoms, alters the preference of their adsorption. This preference for site occupation and altered adsorption may account for the improved selectivity over that observed for Cu metal. This study demonstrates an example of a scalable synthesis method of bimetallic surfaces utilized with the mixed oxide precursor having the diversity of metal choice, which may drastically alter the electrocatalytic performance, as presented herein.

Estimation of nocturnal CO2 and N2O soil emissions from changes in surface boundary layer mass storage

Science.gov (United States)

Grant, Richard H.; Omonode, Rex A.

2018-04-01

Annual budgets of greenhouse and other trace gases require knowledge of the emissions throughout the year. Unfortunately, emissions into the surface boundary layer during stable, calm nocturnal periods are not measurable using most micrometeorological methods due to non-stationarity and uncoupled flow. However, during nocturnal periods with very light winds, carbon dioxide (CO2) and nitrous oxide (N2O) frequently accumulate near the surface and this mass accumulation can be used to determine emissions. Gas concentrations were measured at four heights (one within and three above canopy) and turbulence was measured at three heights above a mature 2.5 m maize canopy from 23 July to 10 September 2015. Nocturnal CO2 and N2O fluxes from the canopy were determined using the accumulation of mass within a 6.3 m control volume and out the top of the control volume within the nocturnal surface boundary layer. Diffusive fluxes were estimated by flux gradient method. The total accumulative and diffusive fluxes during near-calm nights (friction velocities CO2 and 0.53 nmol m-2 s-1 N2O. Fluxes were also measured using chambers. Daily mean CO2 fluxes determined by the accumulation method were 90 to 130 % of those determined using soil chambers. Daily mean N2O fluxes determined by the accumulation method were 60 to 80 % of that determined using soil chambers. The better signal-to-noise ratios of the chamber method for CO2 over N2O, non-stationary flow, assumed Schmidt numbers, and anemometer tilt were likely contributing reasons for the differences in chambers versus accumulated nocturnal mass flux estimates. Near-surface N2O accumulative flux measurements in more homogeneous regions and with greater depth are needed to confirm the conclusion that mass accumulation can be effectively used to estimate soil emissions during nearly calm nights.

Study of plasma formation in CW CO2 laser beam-metal surface interaction

Science.gov (United States)

Azharonok, V. V.; Vasilchenko, Zh V.; Golubev, Vladimir S.; Gresev, A. N.; Zabelin, Alexandre M.; Chubrik, N. I.; Shimanovich, V. D.

1994-04-01

An interaction of the cw CO2 laser beam and a moving metal surface has been studied. The pulsed and thermodynamical parameters of the surface plasma were investigated by optical and spectroscopical methods. The subsonic radiation wave propagation in the erosion plasma torch has been studied.

Characterization of Qatar's surface carbonates for CO2 capture and thermochemical energy storage

Science.gov (United States)

Kakosimos, Konstantinos E.; Al-Haddad, Ghadeer; Sakellariou, Kyriaki G.; Pagkoura, Chrysa; Konstandopoulos, Athanasios G.

2017-06-01

Samples of surface carbonates were collected from three different areas of the Qatar peninsula. We employed material characterization techniques to examine the morphology and composition of the samples, while their CO2 capture capacity was assessed via multiple successive calcination-carbonation cycles. Our samples were mainly calcite and dolomite based. Calcite samples showed higher initial capacity of around 11 mmol CO2 g-1 which decayed rapidly to less than 2 mmol CO2 g-1. On the other hand, dolomite samples showed an excellent stability (˜15 cycles) with a capacity of 6 mmol CO2 g-1. The performance of the dolomite samples is better compared to other similar natural samples, from literature. A promising result for future studies towards improving their performance by physical and chemical modification.

Estimating surface pCO2 in the northern Gulf of Mexico: Which remote sensing model to use?

Science.gov (United States)

Chen, Shuangling; Hu, Chuanmin; Cai, Wei-Jun; Yang, Bo

2017-12-01

Various approaches and models have been proposed to remotely estimate surface pCO2 in the ocean, with variable performance as they were designed for different environments. Among these, a recently developed mechanistic semi-analytical approach (MeSAA) has shown its advantage for its explicit inclusion of physical and biological forcing in the model, yet its general applicability is unknown. Here, with extensive in situ measurements of surface pCO2, the MeSAA, originally developed for the summertime East China Sea, was tested in the northern Gulf of Mexico (GOM) where river plumes dominate water's biogeochemical properties during summer. Specifically, the MeSAA-predicted surface pCO2 was estimated by combining the dominating effects of thermodynamics, river-ocean mixing and biological activities on surface pCO2. Firstly, effects of thermodynamics and river-ocean mixing (pCO2@Hmixing) were estimated with a two-endmember mixing model, assuming conservative mixing. Secondly, pCO2 variations caused by biological activities (ΔpCO2@bio) was determined through an empirical relationship between sea surface temperature (SST)-normalized pCO2 and MODIS (Moderate Resolution Imaging Spectroradiometer) 8-day composite chlorophyll concentration (CHL). The MeSAA-modeled pCO2 (sum of pCO2@Hmixing and ΔpCO2@bio) was compared with the field-measured pCO2. The Root Mean Square Error (RMSE) was 22.94 μatm (5.91%), with coefficient of determination (R2) of 0.25, mean bias (MB) of - 0.23 μatm and mean ratio (MR) of 1.001, for pCO2 ranging between 316 and 452 μatm. To improve the model performance, a locally tuned MeSAA was developed through the use of a locally tuned ΔpCO2@bio term. A multi-variate empirical regression model was also developed using the same dataset. Both the locally tuned MeSAA and the regression models showed improved performance comparing to the original MeSAA, with R2 of 0.78 and 0.84, RMSE of 12.36 μatm (3.14%) and 10.66 μatm (2.68%), MB of 0.00 μatm and - 0

Structural and electronic properties of Mg and Mg-Nb co-doped TiO2 (101) anatase surface

International Nuclear Information System (INIS)

Sasani, Alireza; Baktash, Ardeshir; Mirabbaszadeh, Kavoos; Khoshnevisan, Bahram

2016-01-01

Highlights: • Formation energy of Mg and Mg-Nb co-doped TiO_2 anatase surface (101) is studied. • Effect of Mg defect to the TiO_2 anatase (101) surface and bond length distribution of the surface is studied and it is shown that Mg defects tend to stay far from each other. • Effect of Mg and Nb to the bond length distribution of the surface studied and it is shown that these defects tend to stay close to each other. • Effects of Mg and Mg-Nb defects on DSSCs using TiO_2 anatase hosting these defects are studied. - Abstract: In this paper, by using density functional theory, Mg and Nb-Mg co-doping of TiO_2 anatase (101) surfaces are studied. By studying the formation energy of the defects and the bond length distribution of the surface, it is shown that Mg defects tend to stay as far as possible to induce least possible lattice distortion while Nb and Mg defects stay close to each other to cause less stress to the surface. By investigating band structure of the surface and changes stemmed from the defects, potential effects of Mg and Mg-Nb co-doping of TiO_2 surface on dye-sensitized solar cells are investigated. In this study, it is shown that the Nb-Mg co-doping could increase J_S_C of the surface while slightly decreasing V_O_C compared to Mg doped surface, which might result in an increase in efficiency of the DSSCs compared to Nb or Mg doped surfaces.

High speed surface cleaning by a high repetition rated TEA-CO2 laser

International Nuclear Information System (INIS)

Tsunemi, Akira; Hirai, Ryo; Hagiwara, Kouji; Nagasaka, Keigo; Tashiro, Hideo

1994-01-01

We demonstrated the feasibility of high speed cleaning of solid surfaces by the laser ablation technique using a TEA-CO 2 laser. The laser pulses with the repetition rate of 1 kHz were applied to paint, rust, moss and dirt attached on the surfaces. The attachments were effectively removed without the damage of bulk surfaces by the irradiation of line-focused sequential pulses with an energy of 300 mJ/pulse. A cleaning rate reached to 17 m 2 /hour for the case of paint removal from iron surfaces. (author)

Distribution of the partial pressure of CO2 in surface water (pCO2w) between Japan and the Hawaiian Islands: pCO2w-SST relationship in the winter and summer

International Nuclear Information System (INIS)

Inoue, Hisayuki Y.; Ishii, Masao; Matsueda, Hidekazu; Kawano, Takeshi; Murata, Akihiko; Takasugi, Yoshio

2003-01-01

On the basis of measurements of the partial pressure of carbon dioxide in surface seawater (pCO 2 w) between Japan and the Hawaiian Islands in winter and summer, we examined the relationship between pCO 2 w and the sea surface temperature (SST) in the North Pacific Subtropical Gyre (NPSG). In winter, pCO 2 w correlated well with the SST (0.14-0.24%/deg C), suggesting a monotonous change in the carbonate system. However, in summer, five different pCO 2 w-SST relationships were found in the NPSG (including the Kuroshio Extension) due to changes in the relative contribution of ocean dynamics (upwelling, vertical mixing and advection), biological activity in the absence (very low level) of macro-nutrients and thermodynamics. The increase in pCO 2 w corresponding to a unit increase in the SST from January to July was low (<2.5%/deg C) west (leeward side) of the Hawaiian Islands (19-22 deg N, 158-168 deg W) and in the Kuroshio Extension (33-35 deg N, 140-165deg E), and high (3%/deg C) south of the Kuroshio Extension (25-30 deg N, 180-165 deg W) and the Hawaiian Islands (15-19 deg N, 157-162 deg W). This suggested that the drawdown of dissolved inorganic carbon was affected by the enhanced biological activity due to upwelling events associated with eddies and/or the transport of dissolved nutrients from gyre edges to the interior

Effets des electrons secondaires sur l'ADN

Science.gov (United States)

Boudaiffa, Badia

Les interactions des electrons de basse energie (EBE) representent un element important en sciences des radiations, particulierement, les sequences se produisant immediatement apres l'interaction de la radiation ionisante avec le milieu biologique. Il est bien connu que lorsque ces radiations deposent leur energie dans la cellule, elles produisent un grand nombre d'electrons secondaires (4 x 104/MeV), qui sont crees le long de la trace avec des energies cinetiques initiales bien inferieures a 20 eV. Cependant, il n'y a jamais eu de mesures directes demontrant l'interaction de ces electrons de tres basse energie avec l'ADN, du principalement aux difficultes experimentales imposees par la complexite du milieu biologique. Dans notre laboratoire, les dernieres annees ont ete consacrees a l'etude des phenomenes fondamentaux induits par impact des EBE sur differentes molecules simples (e.g., N2, CO, O2, H2O, NO, C2H 4, C6H6, C2H12) et quelques molecules complexes dans leur phase solide. D'autres travaux effectues recemment sur des bases de l'ADN et des oligonucleotides ont montre que les EBE produisent des bris moleculaires sur les biomolecules. Ces travaux nous ont permis d'elaborer des techniques pour mettre en evidence et comprendre les interactions fondamentales des EBE avec des molecules d'interet biologique, afin d'atteindre notre objectif majeur d'etudier l'effet direct de ces particules sur la molecule d'ADN. Les techniques de sciences des surfaces developpees et utilisees dans les etudes precitees peuvent etre etendues et combinees avec des methodes classiques de biologie pour etudier les dommages de l'ADN induits par l'impact des EBE. Nos experiences ont montre l'efficacite des electrons de 3--20 eV a induire des coupures simple et double brins dans l'ADN. Pour des energies inferieures a 15 eV, ces coupures sont induites par la localisation temporaire d'un electron sur une unite moleculaire de l'ADN, ce qui engendre la formation d'un ion negatif transitoire

Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

Energy Technology Data Exchange (ETDEWEB)

Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

2016-05-30

Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

Observation of ferromagnetic ordering in a stable α -Co (OH) 2 phase grown on a Mo S2 surface

Science.gov (United States)

Debnath, Anup; Bhattacharya, Shatabda; Saha, Shyamal K.

2017-12-01

Because of the potential application of Co (OH) 2 in a magnetic cooling system as a result of its superior magnetocaloric effect many people have investigated magnetic properties of Co (OH) 2 . Unfortunately, most of the works have been carried out on the β -Co (OH) 2 phase due to the fact that the α -Co (OH) 2 phase is very unstable and continuously transformed into the stable β -Co (OH) 2 phase. However, in the present work, using a Mo S2 sheet as a two-dimensional template, we have been able to synthesize a stable α -Co (OH) 2 phase in addition to a β -Co (OH) 2 phase by varying the layer thickness. It is seen that for thinner samples the β phase, while for thicker samples α phase, is grown on the Mo S2 surface. Magnetic measurements are carried out for the samples over the temperature range from 2 to 300 K and it is seen that for the β phase, ferromagnetic ordering with fairly large coercivity (1271 Oe) at 2 K is obtained instead of the usual antiferromagnetism. The most interesting result is the observation of ferromagnetic ordering with a transition temperature (Curie temperature) more than 100 K in the α -Co (OH) 2 phase. Complete saturation in the hysteresis curve under application of very low field having coercivity of ˜162 Oe at 2 K and 60 Oe at 50 K is obtained. A thin stable α -Co (OH) 2 phase grown on Mo S2 surface with very soft ferromagnetic ordering will be very useful as the core material in electromagnets.

CO2-Water-Rock Wettability: Variability, Influencing Factors, and Implications for CO2 Geostorage.

Science.gov (United States)

Iglauer, Stefan

2017-05-16

Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO 2 is captured from large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO 2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO 2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO 2 cannot percolate), (2) residual trapping (where the CO 2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO 2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO 2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO 2 through the rock are strongly influenced by the CO 2 -brine-rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO 2 -wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO 2 -wet. Note that CO 2 -wet surfaces dramatically reduce CO 2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO 2 -wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO 2 -wettability and the

Blowing loop in the EL-4 reactor: CO{sub 2} flow control analogue study; Boucle de soufflage de la centrale EL-4 - regulation du debit CO{sub 2} - etude analogique

Energy Technology Data Exchange (ETDEWEB)

Chazal, G; Merle, J P; Guillemard, B [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Leroy, C; Robin, L; Jacquin, J C; Cornudet, A [Societe INDATOM, France (France)

1966-07-01

This report describes one study which contributed to the construction of the Monts d'Arree nuclear power station: EL-4. The reactor is cooled by a CO{sub 2} current provided by 3 turbo-blower groups. The priming vapour for the turbines is taken at the exit of the main CO{sub 2} - H{sub 2}O exchangers. The operation of EL 4 is based on a high degree of centralization of the controls which attributes an important role to the general regulation circuits. This general regulation includes in particular an internal blowing loop which controls the CO{sub 2} flow. The study of the control of this CO{sub 2} flow is made up of 3 parts: - analogue representation of the reactors cooling circuit and of the turbo blower unit. - first test campaign using the analogue computer describing the natural behaviour of the system in the absence of control. theoretical determination of the regulation factors; definition of the regulation using an analogue computer and second test campaign for recording the performances of the blowing loop. The 4. part of the report deals with the analogue study: analogue equations - development. (authors) [French] Ce rapport prend place parmi les etudes de realisation de la Centrale des Monts d'Arree EL-4. Le reacteur est refroidi par une circulation de CO{sub 2} assuree par 3 groupes turbosoufflantes. La vapeur d'entrainement des turbines est prelevee a la sortie des echangeurs principaux CO{sub 2} - H{sub 2}O. L'exploitation de EL-4 repose sur une centralisation poussee des moyens de controle-commande qui attribue un role essentiel aux circuits de regulation generale. Cette regulation generale comporte en particulier une boucle interne de soufflage qui realise un asservissement du debit de CO{sub 2}. L'etude de cette regulation du debit CO{sub 2} comprend 3 parties: - representation analogique du circuit de refroidissement du reacteur et de l'ensemble turbine-soufflante. - premiere campagne d'essais sur calculateur analogique decrivant le comportement

Carbon-14 exchange between CO2 and CO in the system 14CO2-CO-NOsub(x)(Ar, N2, O2)-quartz vessels

International Nuclear Information System (INIS)

Wawer, A.; Zielinski, M.

1981-01-01

It has been established that the rate of 14 C exchange between CO 2 and CO is diminished in presence of NO and NO 2 . The temperature dependence of the overall rate of exchange and the partial orders in respect to separate components of the exchange mixtures have been determined. The rate dependence on quartz surface has been established and the surface mechanism considered. The inhibiting action NO and NO 2 is explained. At higher pressures the catalytic effect of NO was found and explained. (author)

Surface modification of chitin using ultrasound-assisted and supercritical CO{sub 2} technologies for cobalt adsorption

Energy Technology Data Exchange (ETDEWEB)

Dotto, Guilherme L., E-mail: guilherme_dotto@yahoo.com.br; Cunha, Jeanine M., E-mail: jeaninecunha@gmail.com; Calgaro, Camila O., E-mail: camila.itepjr@gmail.com; Tanabe, Eduardo H., E-mail: edutanabe@yahoo.com.br; Bertuol, Daniel A., E-mail: dbertuol@gmail.com

2015-09-15

Highlights: • Chitin was modified by ultrasound-assisted (UA) and supercritical (SCO{sub 2}) technologies. • Chitin, UA-chitin and SCO{sub 2}-chitin were used as adsorbents for Co(II). • UA and SCO{sub 2} treatments provided increase of 20 and 3 times in chitin surface area. • The Co(II) adsorption capacity increased until 67.8%, using UA-chitin. - Abstract: Ultrasound-assisted (UA) and supercritical CO{sub 2} technologies (SCO{sub 2}) were used to modify the chitin surface and, improve its adsorption characteristics regarding to cobalt. Chitin, before and after the treatments, was characterized by N{sub 2} adsorption isotherms (BET), infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Unmodified and surface modified chitins were used as adsorbents to remove cobalt from aqueous solutions. The adsorption study was performed by equilibrium isotherms and kinetic curves. The chitin particle characteristics, such as, surface area, pore volume and porosity were improved by the UA and SCO{sub 2} treatments. The crystallinity index decreased after the UA and SCO{sub 2} treatments, and also, intense surface modifications were observed. Langmuir and Freundlich models were adequate to represent the adsorption equilibrium. The maximum adsorption capacities were 50.03, 83.94 and 63.08 mg g{sup −1} for unmodified chitin, UA surface modified chitin and SCO{sub 2} surface modified chitin. The adsorption kinetic curves were well represented by the pseudo-second order model. UA and SCO{sub 2} technologies are alternatives to modify the chitin surface and improve its adsorption characteristics.

Functional response of a near-surface soil microbial community to a simulated underground CO2 storage leak.

Science.gov (United States)

Morales, Sergio E; Holben, William E

2013-01-01

Understanding the impacts of leaks from geologic carbon sequestration, also known as carbon capture and storage, is key to developing effective strategies for carbon dioxide (CO2) emissions management and mitigation of potential negative effects. Here, we provide the first report on the potential effects of leaks from carbon capture and storage sites on microbial functional groups in surface and near-surface soils. Using a simulated subsurface CO2 storage leak scenario, we demonstrate how CO2 flow upward through the soil column altered both the abundance (DNA) and activity (mRNA) of microbial functional groups mediating carbon and nitrogen transformations. These microbial responses were found to be seasonally dependent and correlated to shifts in atmospheric conditions. While both DNA and mRNA levels were affected by elevated CO2, they did not react equally, suggesting two separate mechanisms for soil microbial community response to high CO2 levels. The results did not always agree with previous studies on elevated atmospheric (rather than subsurface) CO2 using FACE (Free-Air CO2 Enrichment) systems, suggesting that microbial community response to CO2 seepage from the subsurface might differ from its response to atmospheric CO2 increases.

Effect of atmospheric CO{sub 2} on surface segregation and phase formation in La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ} thin films

Energy Technology Data Exchange (ETDEWEB)

Yu, Yang [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Luo, Heng [Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States); Cetin, Deniz [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Lin, Xi [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States); Ludwig, Karl [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Physics, Boston University, Boston, MA 02215 (United States); Pal, Uday; Gopalan, Srikanth [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States); Basu, Soumendra, E-mail: basu@bu.edu [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States)

2014-12-30

Highlights: • LSCF exhibits Sr surface segregation on high-temperature annealing. • The presence of atmospheric CO{sub 2} enhances the kinetics of Sr surface segregation. • At high-CO{sub 2} partial pressures, there is a significant coverage of the surface by Sr-rich phases. • The increase in kinetics is attributed to increased thermodynamic driving force for SrCO{sub 3} formation. - Abstract: The effects of atmospheric CO{sub 2} on surface segregation and phase formation in La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ} (LSCF-6428) were investigated. (0 0 1)-oriented LSCF-6428 thin films were deposited on lattice matched (1 1 0)-oriented NdGaO{sub 3} (NGO) substrates by pulsed laser deposition (PLD). Using the synchrotron technique of total reflection X-ray fluorescence (TXRF), it was found that the kinetics of Sr surface segregation was enhanced when annealing at 800 °C in a high-CO{sub 2} partial pressure, as compared to a similar anneal in a CO{sub 2}-free atmosphere, with the oxygen partial pressure being constant in both cases. Hard X-ray photoelectron spectroscopy (HAXPES) measurements showed that the contribution of the surface carbonate to surface oxide phases increased significantly for the sample annealed in the high-CO{sub 2} atmosphere. Atomic force microscopy (AFM) studies showed enhanced surface phase formation during the high-CO{sub 2} partial pressure anneal. Density functional theory (DFT) calculations provide a thermodynamic basis for the enhanced kinetics of surface segregation in the presence of atmospheric CO{sub 2}.

Structural and electronic properties of Mg and Mg-Nb co-doped TiO2 (101) anatase surface

Energy Technology Data Exchange (ETDEWEB)

Sasani, Alireza [Department of Science, Karaj Islamic Azad University, Karaj, Alborz, P.O. Box 31485-313 (Iran, Islamic Republic of); Baktash, Ardeshir [Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167 (Iran, Islamic Republic of); Mirabbaszadeh, Kavoos, E-mail: mirabbas@aut.ac.ir [Department of Energy Engineering and Physics, Amirkabir University of Technology, Tehran, P. O. Box 15875-4413 (Iran, Islamic Republic of); Khoshnevisan, Bahram [Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167 (Iran, Islamic Republic of)

2016-10-30

Highlights: • Formation energy of Mg and Mg-Nb co-doped TiO{sub 2} anatase surface (101) is studied. • Effect of Mg defect to the TiO{sub 2} anatase (101) surface and bond length distribution of the surface is studied and it is shown that Mg defects tend to stay far from each other. • Effect of Mg and Nb to the bond length distribution of the surface studied and it is shown that these defects tend to stay close to each other. • Effects of Mg and Mg-Nb defects on DSSCs using TiO{sub 2} anatase hosting these defects are studied. - Abstract: In this paper, by using density functional theory, Mg and Nb-Mg co-doping of TiO{sub 2} anatase (101) surfaces are studied. By studying the formation energy of the defects and the bond length distribution of the surface, it is shown that Mg defects tend to stay as far as possible to induce least possible lattice distortion while Nb and Mg defects stay close to each other to cause less stress to the surface. By investigating band structure of the surface and changes stemmed from the defects, potential effects of Mg and Mg-Nb co-doping of TiO{sub 2} surface on dye-sensitized solar cells are investigated. In this study, it is shown that the Nb-Mg co-doping could increase J{sub SC} of the surface while slightly decreasing V{sub OC} compared to Mg doped surface, which might result in an increase in efficiency of the DSSCs compared to Nb or Mg doped surfaces.

Variations in pCO2 during summer in the surface water of an unproductive lake in northern Sweden

International Nuclear Information System (INIS)

Jonsson, A.; Aaberg, J.; Jansson, M.

2007-01-01

Unproductive lakes are generally supersaturated with carbon dioxide (CO 2 ) and emit CO 2 to the atmosphere continuously during ice-free periods. However, temporal variation of the partial pressure of CO 2 (pCO 2 ) and thus of CO 2 evasion to atmosphere is poorly documented. We therefore carried out temporally high-resolution (every 6 h) measurements of the pCO 2 using an automated logger system in the surface water of a subarctic, unproductive, lake in the birch forest belt. The study period was June-September 2004. We found that the pCO 2 showed large seasonal variation, but low daily variation. The seasonal variation was likely mainly caused by variations in input and mineralization of allochthonous organic matter. Stratification depth probably also influenced pCO 2 of the surface water by controlling the volume in which mineralization of dissolved organic carbon (DOC) occurred. In lakes, with large variations in pCO 2 , as in our study lake a high (weekly) sampling intensity is recommended for obtaining accurate estimates of the evasion of CO 2

An In-Situ Root-Imaging System in the Context of Surface Detection of CO2

Science.gov (United States)

Apple, M. E.; Prince, J. B.; Bradley, A. R.; Zhou, X.; Lakkaraju, V. R.; Male, E. J.; Pickles, W.; Thordsen, J. J.; Dobeck, L.; Cunningham, A.; Spangler, L.

2009-12-01

Carbon sequestration is a valuable method of spatially confining CO2 belowground. The Zero Emissions Research Technology, (ZERT), site is an experimental facility in a former agricultural field on the Montana State University campus in Bozeman, Montana, where CO2 was experimentally released at a rate of 200kg/day in 2009 into a 100 meter underground injection well running parallel to the ground surface. This injection well, or pipe, has deliberate leaks at intervals, and CO2 travels from these leaks upward to the surface of the ground. The ZERT site is a model system designed with the purpose of testing methods of surface detection of CO2. One important aspect of surface detection is the determination of the effects of CO2 on the above and belowground portions of plants growing above sequestration fields. At ZERT, these plants consist of a pre-existing mixture of herbaceous species present at the agricultural field. Species growing at the ZERT site include several grasses, Dactylis glomerata (Orchard Grass), Poa pratensis (Kentucky Bluegrass), and Bromus japonicus (Japanese Brome); the nitrogen-fixing legumes Medicago sativa, (Alfalfa), and Lotus corniculatus, (Birdsfoot trefoil); and an abundance of Taraxacum officinale, (Dandelion). Although the aboveground parts of the plants at high CO2 are stressed, as indicated by changes in hyperspectral plant signatures, leaf fluorescence and leaf chlorophyll content, we are interested in determining whether the roots are also stressed. To do so, we are combining measurements of soil conductivity and soil moisture with root imaging. We are using an in-situ root-imaging system manufactured by CID, Inc. (Camas, WA), along with image analysis software (Image-J) to analyze morphometric parameters in the images and to determine what effects, if any, the presence of leaking and subsequently upwelling CO2 has on the phenology of root growth, growth and turnover of individual fine and coarse roots, branching patterns, and root

On the feasibility of borehole-to-surface electromagnetics for monitoring CO2 sequestration

Science.gov (United States)

Wilson, G. A.; Zhdanov, M. S.; Hibbs, A. D.; Black, N.; Gribenko, A. V.; Cuma, M.; Agundes, A.; Eiskamp, G.

2012-12-01

Carbon capture and storage (CCS) projects rely on storing supercritical CO2 in deep saline reservoirs where buoyancy forces drive the injected CO2 upward into the aquifer until a seal is reached. The permanence of the sequestration depends entirely on the long-term geological integrity of the seal. Active geophysical monitoring of the sequestration is critical for informing CO2 monitoring, accounting and verification (MVA) decisions. During injection, there exists a correlation between the changes in CO2 and water saturations in a saline reservoir. Dissolved salts react with the CO2 to precipitate out as carbonates, thereby generally decreasing the electrical resistivity. As a result, there is a correlation between the change in fluid saturation and measured electromagnetic (EM) fields. The challenge is to design an EM survey appropriate for monitoring large, deep reservoirs. Borehole-to-surface electromagnetic (BSEM) surveys consist of borehole-deployed galvanic transmitters and a surface-based array of electric and magnetic field sensors. During a recent field trial, it was demonstrated that BSEM could successfully identify the oil-water contact in the water-injection zone of a carbonate reservoir. We review the BSEM methodology, and perform full-field BSEM modeling. The 3D resistivity models used in this study are based on dynamic reservoir simulations of CO2 injection into a saline reservoir. Although the electric field response at the earth's surface is low, we demonstrate that it can be accurately measured and processed with novel methods of noise cancellation and sufficient stacking over the period of monitoring to increase the signal-to-noise ratio for subsequent seismic- and well-constrained 3D inversion. For long-term or permanent monitoring, we discuss the deployment of novel electric field sensors with chemically inert electrodes that couple to earth in a capacitive manner. This capacitive coupling is a purely EM phenomenon, which, to first order, has

Decontamination of surfaces by blasting with crystals of H2O and CO2

International Nuclear Information System (INIS)

Benson, C.E.; Parfitt, J.E.; Patton, B.D.

1995-02-01

A major mission of the US Department of Energy during the 1990s is site and environmental cleanup. In pursuit of this mission, numerous remediation projects are under way and many others are being planned at Oak Ridge National Laboratory (ORNL). In this report, tests using two proposed methods for decontaminating surfaces one using water ice crystals [Crystalline Ice Blast (CIB)], the other using dry ice crystals (CO 2 Cleanblast trademark) -- are described. Both methods are adaptations of the commonly used sand blasting technology. The two methods tested differ from sand blasting in that the particles are not particularly abrasive and do not accumulate as particles in the wastes. They differ from each other in that the CO 2 particles sublime during and after impact and the ice particles melt. Thus, the two demonstrations provide important information about two strong candidate decontamination methodologies. Each process was tested at ORNL using contaminated lead bricks and contaminated tools and equipment. Demonstrations with the prototype Crystalline Ice Blast and the CO 2 Cleanblast systems showed that paint, grease, and oil can be removed from metal, plastic, asphalt, and concrete surfaces. Furthermore, removal of contamination from lead bricks was highly effective. Both processes were found to be less effective, under the conditions tested, with contaminated tools and equipment that had chemically bonded contamination or contamination located in crevices since neither technology abrades the substrates or penetrates deeply into crevices to remove particulates. Some process improvements are recommended

Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

Science.gov (United States)

Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

2015-01-01

The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

Activation and dissociation of CO2 on the (001), (011), and (111) surfaces of mackinawite (FeS): A dispersion-corrected DFT study.

Science.gov (United States)

Dzade, N Y; Roldan, A; de Leeuw, N H

2015-09-07

Iron sulfide minerals, including mackinawite (FeS), are relevant in origin of life theories, due to their potential catalytic activity towards the reduction and conversion of carbon dioxide (CO2) to organic molecules, which may be applicable to the production of liquid fuels and commodity chemicals. However, the fundamental understanding of CO2 adsorption, activation, and dissociation on FeS surfaces remains incomplete. Here, we have used density functional theory calculations, corrected for long-range dispersion interactions (DFT-D2), to explore various adsorption sites and configurations for CO2 on the low-index mackinawite (001), (110), and (111) surfaces. We found that the CO2 molecule physisorbs weakly on the energetically most stable (001) surface but adsorbs relatively strongly on the (011) and (111) FeS surfaces, preferentially at Fe sites. The adsorption of the CO2 on the (011) and (111) surfaces is shown to be characterized by significant charge transfer from surface Fe species to the CO2 molecule, which causes a large structural transformation in the molecule (i.e., forming a negatively charged bent CO2 (-δ) species, with weaker C-O confirmed via vibrational frequency analyses). We have also analyzed the pathways for CO2 reduction to CO and O on the mackinawite (011) and (111) surfaces. CO2 dissociation is calculated to be slightly endothermic relative to the associatively adsorbed states, with relatively large activation energy barriers of 1.25 eV and 0.72 eV on the (011) and (111) surfaces, respectively.

Les coûts du diabète sur 10 ans au Canada : intégration des coûts en soins de santé imputables au diabète à un modèle de prédiction de son incidence

Directory of Open Access Journals (Sweden)

Anja Bilandzic

2017-01-01

Full Text Available Introduction : Notre objectif était d’estimer les coûts de santé directs liés au traitement du diabète au Canada sur 10 ans, à l’aide de données de sondages nationaux et d’un outil de prévision du risque de diabète, ainsi que les coûts par personne. Méthodologie : Nous avons utilisé le Diabetes Population Risk Tool pour estimer le nombre de nouveaux cas de diabète chez les personnes âgées de 20 ans et plus sur 10 ans (jusqu'en 2022 à l’aide des données de 2011 et de 2012 de l’Enquête sur la santé dans les collectivités canadiennes. Nous avons évalué les coûts liés au diabète à partir d’une étude de cohorte faisant appel à l’appariement par score de propension, en utilisant la base de données sur le diabète de l’Ontario ainsi que d’autres données administratives. Nous avons calculé les coûts totaux en utilisant les coûts associés aux nouveaux cas, en tenant compte du sexe, de l’année du diagnostic et des taux de mortalité annuels dus à la maladie. Résultats : D'après nos calculs, le risque de développer le diabète sur 10 ans s’élevait pour la population canadienne en 2011-2012 à 9,98 %, soit 2,16 millions de nouveaux cas. Les coûts totaux en soins de santé imputables au diabète pendant cette période sont de 15,36 milliards (7,55 milliards pour les femmes et 7,81 milliards pour les hommes. Ce sont les hospitalisations de courte durée qui constituent la majeure partie de ces coûts (43,2 %. Des interventions menées au sein de la population entraînant une perte de poids de 5 % au sein de la population permettraient de réduire les coûts des soins de santé de 2,03 milliards de dollars. Une réduction du risque de 30 % obtenue grâce à des interventions auprès des personnes à plus haut risque de développer le diabète (c.-à-d. les 10 % au sommet du groupe à risque le plus élevé entraînerait des économies de l’ordrede 1,48 million de dollars. Conclusion : D'ici 2022

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

Science.gov (United States)

Huber, George W.; Upadhye, Aniruddha A.; Kim, Hyung Ju; Ro, Insoo; Tejedor-Anderson, M. Isabel

2017-08-22

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

Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

Science.gov (United States)

Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

2013-05-14

A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

Science.gov (United States)

Rissmann, C.; Christenson, B.; Werner, C.; Leybourne, M.; Cole, J.; Gravley, D.

2012-01-01

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20a of production (116MW e). Soil CO2 degassing was quantified with 2663 CO2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (Wm -2) using published soil temperature heat flow functions. Both CO2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20a of production, current CO2 emissions equated to 111??6.7T/d. Observed heat flow was 70??6.4MW, compared with a pre-production value of 122MW. This 52MW reduction in surface heat flow is due to production-induced drying up of all alkali-Cl outflows (61.5MW) and steam-heated pools (8.6MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali-Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18MW (from 25MW to 43.3??5MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20a of production, with an observed heat flow of 26.7??3MW and a CO 2 emission rate of 39??3T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali-Cl outflows once contributed significantly to the natural surface heat flow (~50%) they contributed little (99% of the original CO 2

Surface properties of poly(acrylonitrile) (PAN) precipitation polymerized in supercritical CO2 and the influence of the molecular weight.

Science.gov (United States)

Shen, Qing; Gu, Qing-Feng; Hu, Jian-Feng; Teng, Xin-Rong; Zhu, Yun-Feng

2003-11-15

In this paper, the surface properties, e.g., the total surface free energy and the related Lifshitz-van der Waals and Lewis acid-base components, of polyacrylonitrile (PAN) precipitation polymerized in supercritical CO(2) have been characterized. Moreover, the influence of molecular weight varying has been also investigated. Results show that the surface properties of PAN resulting from supercritical CO(2) are different from those obtained by the conventional method. Of these data, one important finding is that the supercritical CO(2) PAN seems to decrease the surface free energy with the increased molecular weight. Based on previous recorded NMR spectra of this PAN and especially compared to commercial PAN, such phenomena are discussed and ascribed to an increase of the H-bonds and a reduction of the isotacticity in the supercritical CO(2) condition for PAN.

Surface Ocean CO2 Atlas Database Version 5 (SOCATv5) (NCEI Accession 0163180)

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — The Surface Ocean CO2 Atlas (SOCAT, www.socat.info) is a synthesis activity by the international marine carbon research community and has more than 100 contributors...

Targeted partial surface modification with nano-SiO2@Li2CoPO4F as high-voltage cathode material for LIBs

Science.gov (United States)

Chang, Caiyun; Huang, Zhipeng; Tian, Runsai; Jiang, Xinyu; Li, Chunsheng; Feng, Jijun

2017-10-01

Tuning whole/partial surface modification on cathode material with oxide material is a sought-after method to enhance the electrochemical performance in power storage field. Herein, nano-SiO2 targeted partial surface modified high voltage cathode material Li2CoPO4F has been successfully fabricated via a facile self-assembly process in silica dispersion at ambient temperature. With the aid of polar -OH groups attracted on the surface of SiO2 micelles, the nano-SiO2 preferentially nestle up along the borders and boundaries of Li2CoPO4F particles, where protection should be deployed with emphasis against the undesirable interactions between materials and electrolytes. Compared with pristine Li2CoPO4F, the SiO2 selectively modified Li2CoPO4F cathode materials, especially LCPF-3S, exhibit desirable electrochemical performances with higher discharge capacity, more outstanding cycle stability and favorable rate capability without any additional carbon involved. The greatly enhanced electrochemical properties can be attributed to the improved lithium-ion diffusion kinetics and structure tolerance during repeated lithiation/delithiation process. Such findings reveal a great potential of nano-SiO2 modified Li2CoPO4F as high energy cathode material for lithium ion batteries.

Possibilities of a metal surface radioactive decontamination using a pulsed CO2 laser

Science.gov (United States)

Milijanic, Scepan S.; Stjepanovic, Natasa N.; Trtica, Milan S.

2000-01-01

There is a growing interest in the laser radioactive decontamination of metal surfaces. It offers advantages over conventional methods: improved safety, reduction of secondary waste, reduced waste volume, acceptable cost. A main mechanism of cleaning in by lasers is ablation. In this work a pulsed TEA CO2 laser was used for surface cleaning, primarily in order to demonstrate that the ablation from metal surfaces with this laser is possible even with relatively low pulse energies, and secondary, that it could be competitive with other lasers because of much higher energy efficiencies. The laser pulse contains two parts, one strong and shot peak at the beginning, followed with a tail. The beam was focused onto a contaminated surface with a KBr lens. The surface was contaminated with 137Cs. Three different metals were used: stainless steel, copper and aluminum. The evaporated material was pumped out in air atmosphere and transferred to a filter. Presence of the activity on the filter was proved by a germanium detector-multichannel analyzer. Activity levels were measured by a GM counter. Calculated decontamination factors as well as collection factors have shown that ablation takes place with relatively high efficiency of decontamination. This investigation suggests that decontamination using the CO2 laser should be seriously considered.

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

Science.gov (United States)

Fu, Wen Gan

2018-05-02

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

How secure is subsurface CO2 storage? Controls on leakage in natural CO2 reservoirs

Science.gov (United States)

Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, Stuart

2014-05-01

Carbon Capture and Storage (CCS) is the only industrial scale technology available to directly reduce carbon dioxide (CO2) emissions from fossil fuelled power plants and large industrial point sources to the atmosphere. The technology includes the capture of CO2 at the source and transport to subsurface storage sites, such as depleted hydrocarbon reservoirs or saline aquifers, where it is injected and stored for long periods of time. To have an impact on the greenhouse gas emissions it is crucial that there is no or only a very low amount of leakage of CO2 from the storage sites to shallow aquifers or the surface. CO2 occurs naturally in reservoirs in the subsurface and has often been stored for millions of years without any leakage incidents. However, in some cases CO2 migrates from the reservoir to the surface. Both leaking and non-leaking natural CO2 reservoirs offer insights into the long-term behaviour of CO2 in the subsurface and on the mechanisms that lead to either leakage or retention of CO2. Here we present the results of a study on leakage mechanisms of natural CO2 reservoirs worldwide. We compiled a global dataset of 49 well described natural CO2 reservoirs of which six are leaking CO2 to the surface, 40 retain CO2 in the subsurface and for three reservoirs the evidence is inconclusive. Likelihood of leakage of CO2 from a reservoir to the surface is governed by the state of CO2 (supercritical vs. gaseous) and the pressure in the reservoir and the direct overburden. Reservoirs with gaseous CO2 is more prone to leak CO2 than reservoirs with dense supercritical CO2. If the reservoir pressure is close to or higher than the least principal stress leakage is likely to occur while reservoirs with pressures close to hydrostatic pressure and below 1200 m depth do not leak. Additionally, a positive pressure gradient from the reservoir into the caprock averts leakage of CO2 into the caprock. Leakage of CO2 occurs in all cases along a fault zone, indicating that

Segregation of O2 and CO on the surface of dust grains determines the desorption energy of O2

Science.gov (United States)

Noble, J. A.; Diana, S.; Dulieu, F.

2015-12-01

Selective depletion towards pre-stellar cores is still not understood. The exchange between the solid and gas phases is central to this mystery. The aim of this paper is to show that the thermal desorption of O2 and CO from a submonolayer mixture is greatly affected by the composition of the initial surface population. We have performed thermally programmed desorption (TPD) experiments on various submonolayer mixtures of O2 and CO. Pure O2 and CO exhibit almost the same desorption behaviour, but their desorption differs strongly when mixed. Pure O2 is slightly less volatile than CO, while in mixtures, O2 desorbs earlier than CO. We analyse our data using a desorption law linking competition for binding sites with desorption, based on the assumption that the binding energy distribution of both molecules is the same. We apply Fermi-Dirac statistics in order to calculate the adsorption site population distribution, and derive the desorbing fluxes. Despite its simplicity, the model reproduces the observed desorption profiles, indicating that competition for adsorption sites is the reason for lower temperature O2 desorption. CO molecules push-out or `dislodge' O2 molecules from the most favourable binding sites, ultimately forcing their early desorption. It is crucial to consider the surface coverage of dust grains in any description of desorption. Competition for access to binding sites results in some important discrepancies between similar kinds of molecules, such as CO and O2. This is an important phenomenon to be investigated in order to develop a better understanding of the apparently selective depletion observed in dark molecular clouds.

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

International Nuclear Information System (INIS)

Rissmann, Clinton; Christenson, Bruce; Werner, Cynthia; Leybourne, Matthew; Cole, Jim; Gravley, Darren

2012-01-01

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW e ). Soil CO 2 degassing was quantified with 2663 CO 2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m −2 ) using published soil temperature heat flow functions. Both CO 2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO 2 emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO 2 emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they

Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

Science.gov (United States)

Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

2018-01-01

Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

Facile synthesis of surface N-doped Bi{sub 2}O{sub 2}CO{sub 3}: Origin of visible light photocatalytic activity and in situ DRIFTS studies

Energy Technology Data Exchange (ETDEWEB)

Zhou, Ying, E-mail: yzhou@swpu.edu.cn [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); Insititute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany); Zhao, Ziyan [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); Wang, Fang; Cao, Kun [The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); Doronkin, Dmitry E. [Insititute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany); Dong, Fan [College of Environmental and Biological Engineering, Chonqing Technology and Business University, Chongqing 400067 (China); Grunwaldt, Jan-Dierk, E-mail: grunwaldt@kit.edu [Insititute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany)

2016-04-15

Graphical abstract: Surfactant (CTAB) can induce nitrogen interstitially doping in the Bi{sub 2}O{sub 2}CO{sub 3} surface, leading to the formation of localized states from N−O bond, which probably account for the origin of the visible light activity. Moreover, the photocatalytic NO oxidation processes over Bi{sub 2}O{sub 2}CO{sub 3} were successfully monitored for the first time by in situ DRIFTS. - Highlights: • Interstitially doping N in the Bi{sub 2}O{sub 2}CO{sub 3} surface was achieved at room temperature. • N-doped Bi{sub 2}O{sub 2}CO{sub 3} exhibited significantly enhanced visible light photocatalytic activity compared to the pristine Bi{sub 2}O{sub 2}CO{sub 3}. • The formation of localized states from N−O bond could account for the visible light activity of Bi{sub 2}O{sub 2}CO{sub 3}. • The photocatalytic NO oxidation process was monitored by in situ DRIFTS. - Abstract: Bi{sub 2}O{sub 2}CO{sub 3} nanosheets with exposed {001} facets were prepared by a facile room temperature chemical method. Due to the high oxygen atom density in {001} facets of Bi{sub 2}O{sub 2}CO{sub 3}, the addition of cetyltrimethylammonium bromide (CTAB) does not only influence the growth of crystalline Bi{sub 2}O{sub 2}CO{sub 3}, but also modifies the surface properties of Bi{sub 2}O{sub 2}CO{sub 3} through the interaction between CTAB and Bi{sub 2}O{sub 2}CO{sub 3}. Nitrogen from CTAB as dopant interstitially incorporates in the Bi{sub 2}O{sub 2}CO{sub 3} surface evidenced by both experimental and theoretical investigations. Hence, the formation of localized states from N−O bond improves the visible light absorption and charge separation efficiency, which leads to an enhancement of visible light photocatalytic activity toward to the degradation of Rhodamine B (RhB) and oxidation of NO. In addition, the photocatalytic NO oxidation over Bi{sub 2}O{sub 2}CO{sub 3} nanosheets was successfully monitored for the first time using in situ diffuse reflectance infrared Fourier

Role of CO2 in the oxy-dehydrogenation of ethylbenzene to styrene on the CeO2(111) surface

Science.gov (United States)

Fan, Hong-Xia; Feng, Jie; Li, Wen-Ying; Li, Xiao-Hong; Wiltowski, Tomasz; Ge, Qing-Feng

2018-01-01

The role of CO2 in the ethylbenzene oxy-dehydrogenation to styrene on the CeO2(111) surface was thoroughly investigated by the density functional theory (DFT) calculations. Results show that the first Csbnd H bond of ethylbenzene is activated via the oxo-insertion with a barrier of 1.70 eV, resulting in a 2-phenylethyl species and an H atom adsorbed on two-adjacent-lattice oxygen. The H adatom forms a hydroxyl-like species (denoted as O*H). The subsequent dehydrogenation to styrene can be assisted by either the next lattice oxygen (pathway R1) or the O*H species (pathway R2). The two pathways have almost the same activation energy (0.84 eV for R1 and 0.85 eV for R2), forming a new O*H and desorbing a H2O molecule while leaving an oxygen vacancy on the surface, respectively. In the presence of CO2, it will react with O*H through the reverse water gas shift reaction with an activation barrier of 0.98 eV and reaction energy of 0.30 eV. The reverse water gas shift reaction helps to clear the H adatoms from the lattice oxygen, thereby competing with styrene formation via pathway R2. However, the activation energy following the reverse water gas shift mechanism is 0.13 eV higher than that of styrene formation via pathway R2. Therefore, the formation of oxygen vacancy cannot be inhibited, while CO2 can react with the surface oxygen vacancy to produce CO with a high activation energy of 2.10 eV.

Impact of membrane lung surface area and blood flow on extracorporeal CO2 removal during severe respiratory acidosis.

Science.gov (United States)

Karagiannidis, Christian; Strassmann, Stephan; Brodie, Daniel; Ritter, Philine; Larsson, Anders; Borchardt, Ralf; Windisch, Wolfram

2017-12-01

Veno-venous extracorporeal CO 2 removal (vv-ECCO 2 R) is increasingly being used in the setting of acute respiratory failure. Blood flow rates through the device range from 200 ml/min to more than 1500 ml/min, and the membrane surface areas range from 0.35 to 1.3 m 2 . The present study in an animal model with similar CO 2 production as an adult patient was aimed at determining the optimal membrane lung surface area and technical requirements for successful vv-ECCO 2 R. Four different membrane lungs, with varying lung surface areas of 0.4, 0.8, 1.0, and 1.3m 2 were used to perform vv-ECCO 2 R in seven anesthetized, mechanically ventilated, pigs with experimentally induced severe respiratory acidosis (pH 7.0-7.1) using a 20Fr double-lumen catheter with a sweep gas flow rate of 8 L/min. During each experiment, the blood flow was increased stepwise from 250 to 1000 ml/min. Amelioration of severe respiratory acidosis was only feasible when blood flow rates from 750 to 1000 ml/min were used with a membrane lung surface area of at least 0.8 m 2 . Maximal CO 2 elimination was 150.8 ml/min, with pH increasing from 7.01 to 7.30 (blood flow 1000 ml/min; membrane lung 1.3 m 2 ). The membrane lung with a surface of 0.4 m 2 allowed a maximum CO 2 elimination rate of 71.7 mL/min, which did not result in the normalization of pH, even with a blood flow rate of 1000 ml/min. Also of note, an increase of the surface area above 1.0 m 2 did not result in substantially higher CO 2 elimination rates. The pressure drop across the oxygenator was considerably lower (respiratory acidosis, irrespective of the surface area of the membrane lung being used. The converse was also true, low surface membrane lungs (0.4 m 2 ) were not capable of completely correcting severe respiratory acidosis across the range of blood flows used in this study.

Adsorbed Carbon Formation and Carbon Hydrogenation for CO_2 Methanation on the Ni(111) Surface: ASED-MO Study

International Nuclear Information System (INIS)

Choe, Sang Joon; Kang, Hae Jin; Kim, Su Jin; Park, Sung Bae; Park, Dong Ho; Huh, Do Sung

2005-01-01

Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for CO_2 methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for CO_2 dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of CH_4 the intermediate complex are 1.21 A, 1.31 A for the C···H_(_1_), and 2.82 A for the height, with angles of 105 .deg. for H_(_1_)CH and 98 .deg. for H_(_1_)CH_(_1_)

Case study on ground surface deformation induced by CO2 injection into coal seam

International Nuclear Information System (INIS)

Li Hong; Tang Chun'an

2010-01-01

To monitor a geomechanical response of injecting CO 2 into relatively shallow coal seams, tiltmeters were set as an array to cover the ground surface area surrounding the injection well, and to measure the ground deformation during a well fracturing stimulation and a short-term CO 2 injection test. In this paper, an attempt to establish a quantitative relationship between the in-situ coal swelling and the corresponding ground deformation was made by means of numerical simulation study. (authors)

Characterizing near-surface CO2 conditions before injection - Perspectives from a CCS project in the Illinois Basin, USA

Science.gov (United States)

Locke, R.A.; Krapac, I.G.; Lewicki, J.L.; Curtis-Robinson, E.

2011-01-01

The Midwest Geological Sequestration Consortium is conducting a large-scale carbon capture and storage (CCS) project in Decatur, Illinois, USA to demonstrate the ability of a deep saline formation to store one million tonnes of carbon dioxide (CO2) from an ethanol facility. Beginning in early 2011, CO2 will be injected at a rate of 1,000 tonnes/day for three years into the Mount Simon Sandstone at a depth of approximately 2,100 meters. An extensive Monitoring, Verification, and Accounting (MVA) program has been undertaken for the Illinois Basin Decatur Project (IBDP) and is focused on the 0.65 km2 project site. Goals include establishing baseline conditions to evaluate potential impacts from CO2 injection, demonstrating that project activities are protective of human health and the environment, and providing an accurate accounting of stored CO2. MVA efforts are being conducted pre-, during, and post- CO2 injection. Soil and net CO2 flux monitoring has been conducted for more than one year to characterize near-surface CO2 conditions. More than 2,200 soil CO2 flux measurements have been manually collected from a network of 118 soil rings since June 2009. Three ring types have been evaluated to determine which type may be the most effective in detecting potential CO 2 leakage. Bare soil, shallow-depth rings were driven 8 cm into the ground and were prepared to minimize surface vegetation in and near the rings. Bare soil, deep-depth rings were prepared similarly, but were driven 46 cm. Natural-vegetation, shallow-depth rings were driven 8 cm and are most representative of typical vegetation conditions. Bare-soil, shallow-depth rings had the smallest observed mean flux (1.78 ??mol m-2 s-1) versus natural-vegetation, shallow-depth rings (3.38 ??mol m-2 s-1). Current data suggest bare ring types would be more sensitive to small CO2 leak signatures than natural ring types because of higher signal to noise ratios. An eddy covariance (EC) system has been in use since June

Variations in pCO{sub 2} during summer in the surface water of an unproductive lake in northern Sweden

Energy Technology Data Exchange (ETDEWEB)

Jonsson, A.; Aaberg, J.; Jansson, M. [Dept. of Ecology and Environmental Sci ence, Umeaa Univ., 901 87 Umeaa (Sweden)]. e-mail: anders.jonsson@emg.umu.se

2007-11-15

Unproductive lakes are generally supersaturated with carbon dioxide (CO{sub 2}) and emit CO{sub 2} to the atmosphere continuously during ice-free periods. However, temporal variation of the partial pressure of CO{sub 2} (pCO{sub 2}) and thus of CO{sub 2} evasion to atmosphere is poorly documented. We therefore carried out temporally high-resolution (every 6 h) measurements of the pCO{sub 2} using an automated logger system in the surface water of a subarctic, unproductive, lake in the birch forest belt. The study period was June-September 2004. We found that the pCO{sub 2} showed large seasonal variation, but low daily variation. The seasonal variation was likely mainly caused by variations in input and mineralization of allochthonous organic matter. Stratification depth probably also influenced pCO{sub 2} of the surface water by controlling the volume in which mineralization of dissolved organic carbon (DOC) occurred. In lakes, with large variations in pCO{sub 2}, as in our study lake a high (weekly) sampling intensity is recommended for obtaining accurate estimates of the evasion of CO{sub 2}.

Reaction of Br2 with adsorbed CO on Pt, studied by the surface interrogation mode of scanning electrochemical microscopy.

Science.gov (United States)

Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

2009-12-02

Scanning electrochemical microscopy surface interrogation (SI-SECM) in the cyclic voltammetry mode was successfully used to detect and quantify adsorbed CO on a Pt electrode by reaction with electrogenerated Br(2). The two-electrode setup used in this new technique allowed the production of Br(2) on an interrogator tip, which reported a transient positive feedback above a Pt substrate at open circuit as an indication of the reactivity of this halogen with CO((ads)). Br(-) and CO(2) are shown to be the main products of the reaction (in the absence of O(2)), which may involve the formation of bromophosgene as a hydrolyzable intermediate. Under saturation conditions, CO((ads)) was reproducibly quantified at the polycrystalline Pt surface with theta(CO) approximately = 0.5. The reaction is shown to be blocked by the action of pre-adsorbed cyanide, which demonstrates the surface character of the process. The formation of CO(2) as an end product was further tested in a bulk experiment: addition of Pt black to a mixture of Br(2) in 0.5 M H(2)SO(4) through which CO was bubbled gave a precipitate of BaCO(3) in a saturated solution of Ba(OH)(2). The use of SI-SECM allowed access to a reaction that would otherwise be difficult to prove through conventional electrochemistry on a single electrode.

Instrument for continuous supervision of the radioactivity of CO{sub 2} coolant in piles - DCCA -CO{sub 2} (1960); Dispositif de controle continu de la radioactivite du CO{sub 2} de refroidissement des piles - DCCA - CO{sub 2} (1960)

Energy Technology Data Exchange (ETDEWEB)

Fitoussi, L. [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

1960-07-01

. Dans la seconde partie sont presentes des calculs theoriques en particulier sur la determination du courant d'ionisation dans une chambre d'ionisation a circulation. Cette determination tient compte de plusieurs parametres tels que la moyenne des parcours des particules {beta} dans la chambre d'ionisation, le nombre lineique de paires d'ions formees dans le gaz par ces particules {beta} en fonction de leur energie, la temperature et la pression du gaz dans la chambre d'ionisation. Dans cette meme partie sont evaluees les plages de sensibilite de l'appareillage pour les mesures dans le CO{sub 2} de refroidissement des concentrations de gaz radioactifs tels que l'argon-41 et les gaz de fission de I'uranium-235. Dans la derniere partie, sont presentes les resultats des mesures effectuees avec un tel dispositif aupres de la pile EL2, les etudes particulieres effectuees sur le CO{sub 2} de refroidissement de cette pile, les enseignements tires pendant les fonctionnement normaux et les accidents ainsi qu'une breve presentation du DCCA-CO{sub 2} qui vient d'etre mis en service a G2. La conclusion souligne les possibilites d'utilisation offertes par cet appareil. (auteur)

Instrument for continuous supervision of the radioactivity of CO{sub 2} coolant in piles - DCCA -CO{sub 2} (1960); Dispositif de controle continu de la radioactivite du CO{sub 2} de refroidissement des piles - DCCA - CO{sub 2} (1960)

Energy Technology Data Exchange (ETDEWEB)

Fitoussi, L [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

1960-07-01

partie sont presentes des calculs theoriques en particulier sur la determination du courant d'ionisation dans une chambre d'ionisation a circulation. Cette determination tient compte de plusieurs parametres tels que la moyenne des parcours des particules {beta} dans la chambre d'ionisation, le nombre lineique de paires d'ions formees dans le gaz par ces particules {beta} en fonction de leur energie, la temperature et la pression du gaz dans la chambre d'ionisation. Dans cette meme partie sont evaluees les plages de sensibilite de l'appareillage pour les mesures dans le CO{sub 2} de refroidissement des concentrations de gaz radioactifs tels que l'argon-41 et les gaz de fission de I'uranium-235. Dans la derniere partie, sont presentes les resultats des mesures effectuees avec un tel dispositif aupres de la pile EL2, les etudes particulieres effectuees sur le CO{sub 2} de refroidissement de cette pile, les enseignements tires pendant les fonctionnement normaux et les accidents ainsi qu'une breve presentation du DCCA-CO{sub 2} qui vient d'etre mis en service a G2. La conclusion souligne les possibilites d'utilisation offertes par cet appareil. (auteur)

Optimization of CO2 Laser Cutting Process using Taguchi and Dual Response Surface Methodology

Directory of Open Access Journals (Sweden)

M. Madić

2014-09-01

Full Text Available Selection of optimal cutting parameter settings for obtaining high cut quality in CO2 laser cutting process is of great importance. Among various analytical and experimental optimization methods, the application of Taguchi and response surface methodology is one of most commonly used for laser cutting process optimization. Although the concept of dual response surface methodology for process optimization has been used with success, till date, no experimental study has been reported in the field of laser cutting. In this paper an approach for optimization of CO2 laser cutting process using Taguchi and dual response surface methodology is presented. The goal was to determine the near optimal laser cutting parameter values in order to ensure robust condition for minimization of average surface roughness. To obtain experimental database for development of response surface models, Taguchi’s L25 orthogonal array was implemented for experimental plan. Three cutting parameters, the cutting speed (3, 4, 5, 6, 7 m/min, the laser power (0.7, 0.9, 1.1, 1.3, 1.5 kW, and the assist gas pressure (3, 4, 5, 6, 7 bar, were used in the experiment. To obtain near optimal cutting parameters settings, multi-stage Monte Carlo simulation procedure was performed on the developed response surface models.

Surface properties of Co-doped BaFe{sub 2}As{sub 2} thin films deposited on MgO with Fe buffer layer and CaF{sub 2} substrates

Energy Technology Data Exchange (ETDEWEB)

Sobota, R. [Department of Experimental Physics, FMPI, Comenius University, 842 48 Bratislava (Slovakia); Plecenik, T., E-mail: tomas.plecenik@fmph.uniba.sk [Department of Experimental Physics, FMPI, Comenius University, 842 48 Bratislava (Slovakia); Gregor, M.; Truchly, M.; Satrapinskyy, L.; Vidis, M.; Secianska, K. [Department of Experimental Physics, FMPI, Comenius University, 842 48 Bratislava (Slovakia); Kurth, F.; Holzapfel, B.; Iida, K. [Institute for Metallic Materials, IFW Dresden, PO Box 270116, D-01171 Dresden (Germany); Kus, P.; Plecenik, A. [Department of Experimental Physics, FMPI, Comenius University, 842 48 Bratislava (Slovakia)

2014-09-01

Highlights: • Surfaces of Co-doped Ba-122 films on various substrates were studied. • Substrate influences topography and surface conductivity distribution of the films. • Surface conductivity of Co-doped Ba-122 is highly inhomogeneous. • Point contact spectroscopy results can be affected by the surface differences. - Abstract: Surface properties of Co-doped BaFe{sub 2}As{sub 2} (Ba-122) thin films prepared by pulsed laser deposition on MgO with Fe buffer layer and CaF{sub 2} substrates were inspected by atomic force microscopy, scanning spreading resistance microscopy, scanning tunneling microscopy, X-ray photoelectron spectroscopy, auger electron spectroscopy/microscopy and point contact spectroscopy (PCS). Selected PCS spectra were fitted by extended 1D BTK model. The measurements were done on as-received as well as ion beam etched surfaces. Our results show that the substrate is considerably influencing the surface properties of the films, particularly the topography and surface conductivity distribution, what can affect results obtained by surface-sensitive techniques like PCS.

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

Science.gov (United States)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Surface energy balances of three general circulation models: Current climate and response to increasing atmospheric CO2

International Nuclear Information System (INIS)

Gutowski, W.J.; Gutzler, D.S.; Portman, D.; Wang, W.C.

1988-04-01

The surface energy balance simulated by state-of-the-art general circulation models at GFDL, GISS and NCAR for climates with current levels of atmospheric CO 2 concentration (control climate) and with twice the current levels. The work is part of an effort sponsored by the US Department of Energy to assess climate simulations produced by these models. The surface energy balance enables us to diagnose differences between models in surface temperature climatology and sensitivity to doubling CO 2 in terms of the processes that control surface temperature. Our analysis compares the simulated balances by averaging the fields of interest over a hierarchy of spatial domains ranging from the entire globe down to regions a few hundred kilometers across

Feasibility of Seismic Monitoring at a Potential CO2 Injection Test Site in the Paris Basin Évaluation des apports de la sismique à la surveillance d’un test d’injection de CO2 sur un site pilote potentiel du Bassin de Paris

Directory of Open Access Journals (Sweden)

Becquey M.

2009-09-01

Full Text Available Seismic effects of the injection of CO2 into a partially depleted oil field have been evaluated. Seismic modelling yields small time-lapse effects, including 0.4 ms time-shifts and 4 to 6% amplitude variations at the top and bottom of the reservoir. Amplitude variations at the reservoir level should be slightly larger at large incidence angles, but wave equation modelling shows that picking these reflections will not be easy, because of the presence of shear waves generated at upper interfaces. In-situ fracturation generates azimuthal anisotropy with velocity and amplitude variations with the propagation direction. These variations bear some information about the crack density, about the relation between the fracture nets and the porous medium, and about the fluid content in the pores and fractures. All these effects are however weak and their measurement requires careful seismic data acquisition and processing. Les effets sismiques de l’injection de dioxyde de carbone dans un gisement de petrole deplete ont fait l’objet d’une simulation. Ces effets sont faibles. On peut s’attendre a une variation des temps d’arrivee des reflexions sur des interfaces situees en dessous des reservoirs, de l’ordre de la demi-milliseconde, et a une variation d’amplitude au toit et au mur du reservoir de l’ordre de 6 %. La variation d’amplitude sera legerement plus forte pour les reflexions a grand deport, mais le pointe des reflexions et la mesure des amplitudes seront probablement plus difficiles, en raison de la presence d’ondes converties. La mesure de l’anisotropie azimutale, due a la presence de fractures, peut nous donner des informations sur l’etat de fracturation du reservoir et sur la connexion entre ces fractures et la matrice poreuse. La mesure de ces variations subtiles necessitera une acquisition soignee et un traitement precautionneux des donnees.

Ultra violet photoemission studies of CO2 and NO adsorbed on W(100) surface

International Nuclear Information System (INIS)

Bhattacharya, A.K.; Broughton, J.Q.; Perry, D.L.

1978-01-01

In the last few years ultra violet photoelectron spectroscopy (UPS) has been successfully empolyed to determine the nature and bonding of the species formed when gases absorb on metal surfaces. This information is necessary to understand the mechanism of hetergeneous catalysis. The present report deals with UPS investigation of the chemisorption of CO 2 and NO on a W(100) surface. (Auth.)

Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex

Energy Technology Data Exchange (ETDEWEB)

Nasri, Sameh; Ajili, Yosra [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Jaidane, Nejm-Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Kalugina, Yulia N. [Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation); Halvick, Philippe; Stoecklin, Thierry [Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex (France); Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

2015-05-07

Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is mapped along the intermonomer coordinates. An analytic fit of this 4D-PES is performed. Our extensive computations confirm that the most stable form corresponds to a T-shape structure where the nitrogen molecule points towards the carbon atom of CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} dissociation limit. This 4D-PES is flat and strongly anisotropic along the intermonomer coordinates. This results in the possibility of the occurrence of large amplitude motions within the complex, such as the inversion of N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO(2) electroreduction

DEFF Research Database (Denmark)

Tang, Wei; Peterson, Andrew A; Varela Gasque, Ana Sofia

2012-01-01

This communication examines the effect of the surface morphology of polycrystalline copper on electroreduction of CO(2). We find that a copper nanoparticle covered electrode shows better selectivity towards hydrocarbons compared with the two other studied surfaces, an electropolished copper elect...

A first principles study of interactions of CO{sub 2} with surfaces of a Cu(benzene‐1,3,5‐tricarboxylate) metal organic framework

Energy Technology Data Exchange (ETDEWEB)

Li, Jie, E-mail: jl3336@drexel.edu [Department of Materials Science & Engineering, Drexel University, Philadelphia, PA 19104 (United States); Zhu, Chenming [CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210 (China); Qiao, Zhen [Department of Chemistry, Drexel University, Philadelphia, PA 19104 (United States); Chen, Xinqing; Wei, Wei [CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210 (China); Ji, Haifeng [CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210 (China); Department of Chemistry, Drexel University, Philadelphia, PA 19104 (United States); Sohlberg, Karl [Department of Materials Science & Engineering, Drexel University, Philadelphia, PA 19104 (United States); Department of Chemistry, Drexel University, Philadelphia, PA 19104 (United States)

2016-11-01

Highlights: • DFT calculations are reported for a new Cu(benzene 1,3,5 tricarboxylate) MOF. • Neither of two low-index surfaces displays appreciable surface relaxation. • Strongest CO{sub 2} binding is to surface-exposed aryl groups. • Surface-exposed Cu atoms do not bind CO{sub 2} strongly, even if unsaturated. • Fitting the BET isotherm yields a binding energy in agreement with DFT calculations. - Abstract: Density functional theory is used to investigate the interaction of CO{sub 2} with the 100 and 010 surfaces of a Cu(benzene 1,3,5 tricarboxylate) metal organic framework. The calculation method is first validated by applying it to similar systems for which reliable results have been reported in literature and verifying that consistent results are obtained. The method is then applied to the Cu(benzene 1,3,5 tricarboxylate) system. The results show that neither the 100 or 010 surface undergoes major surface relaxation or surface reconstruction during structural optimization. CO{sub 2} adsorption calculations show that on the 100 surface, the CO{sub 2} molecule interacts with the surface benzene ring through π-π interaction. On the 010 surface, the interaction between the CO{sub 2} and the surface is again dominated by dispersion. Population analysis shows that a Cu atom on the 010 surface, even when nominally coordinatively unsaturated, is not electron deficient, which explains why CO{sub 2} does not bind to it chemically. Adsorption of multiple CO{sub 2} molecules on the 100 surface was also studied to investigate the dependence of the interaction on surface coverage. Least squares fitting of experimental adsorption versus pressure data to the BET isotherm model yields a binding energy in good agreement with the first-principles calculations.

Effet de la substitution du cuivre par du lithium sur les proprietes de l'oxyde spinelle lithium(x)cuivre(y-x)cobalt(3-y)oxygen(4) etudie pour l'electrocatalyse de la reaction de degagement de l'oxygene en milieu alcalin

Science.gov (United States)

Fatih, Khalid

L'electrolyse de l'eau demeure la seule technologie industrielle de generation de l'hydrogene et de l'oxygene tres purs sans rejet de CO2 dans l'atmosphere, ce qui le rend tres attrayant par rapport a la combustion de carburants fossiles qui provoque presentement de serieux problemes environnementaux. Dans le but d'ameliorer le rendement de ce procede, nous avons developpe de nouveaux materiaux d'anode peu couteux, a base de l'oxyde mixte CuyCo3-yO 4, qui possedent une cinetique rapide pour la reaction de degagement de l'oxygene (RDO). Cette reaction suscite un interet particulier en raison de la surtension d'activation relativement elevee a l'anode qui cause la principale perte de rendement du procede. Une etude systematique a ete effectuee sur la substitution du Cu par du Li (0 a 40%), afin d'elucider les proprietes electrocatalytiques des oxydes LixCuy-xCo3-yO4. Ces oxydes, prepares sous forme de poudres par decomposition thermique des nitrates precurseurs entre 300 et 500°C, ont montre (DRX et FTIR) une structure spinelle inverse non-stcechiometrique avec une diminution du volume de la maille cristalline. La surface specifique par BET est d'environ 6 m2 g-1. Le pcn, obtenu par titrage acido-basique, a indique une diminution de la force du lien M-OH avec le taux du Li dans l'oxyde. Les analyses par XPS, realisees sur des films d'oxyde prepares par nebulisation reactive sur un substrat lisse de nickel, revelent un enrichissement de la surface en Cu a partir de 30% Li, et la presence des cations de surface Co2+, Co3+, Cu +, Cu2+ et Cu3+. La concentration de ce dernier montre un maximum a 10 et 20% Li. Suite a la substitution du Cu par du Li, la compensation de la charge serait assuree principalement par la formation d'especes Cu3+ pour les oxydes contenant jusqu'a 20% Li, et par la formation d'especes Co3+ aux taux de substitution superieurs. Les micrographies MEB montrent une morphologie hemispherique des particules d'oxyde reparties uniformement sur le substrat

A shallow subsurface controlled release facility in Bozeman, Montana, USA, for testing near surface CO2 detection techniques and transport models

Energy Technology Data Exchange (ETDEWEB)

Spangler, Lee H.; Dobeck, Laura M.; Repasky, Kevin S.; Nehrir, Amin R.; Humphries, Seth D.; Barr, Jamie L.; Keith, Charlie J.; Shaw, Joseph A.; Rouse, Joshua H.; Cunningham, Alfred B.; Benson, Sally M.; Oldenburg, Curtis M.; Lewicki, Jennifer L.; Wells, Arthur W.; Diehl, J. R.; Strazisar, Brian; Fessenden, Julianna; Rahn, Thom A.; Amonette, James E.; Barr, Jonathan L.; Pickles, William L.; Jacobson, James D.; Silver, Eli A.; Male, Erin J.; Rauch, Henry W.; Gullickson, Kadie; Trautz, Robert; Kharaka, Yousif; Birkholzer, Jens; Wielopolski, Lucien

2010-03-01

A facility has been constructed to perform controlled shallow releases of CO2 at flow rates that challenge near surface detection techniques and can be scalable to desired retention rates of large scale CO2 storage projects. Preinjection measurements were made to determine background conditions and characterize natural variability at the site. Modeling of CO2 transport and concentration in saturated soil and the vadose zone was also performed to inform decisions about CO2 release rates and sampling strategies. Four releases of CO2 were carried out over the summer field seasons of 2007 and 2008. Transport of CO2 through soil, water, plants, and air was studied using near surface detection techniques. Soil CO2 flux, soil gas concentration, total carbon in soil, water chemistry, plant health, net CO2 flux, atmospheric CO2 concentration, movement of tracers, and stable isotope ratios were among the quantities measured. Even at relatively low fluxes, most techniques were able to detect elevated levels of CO2 in the soil, atmosphere, or water. Plant stress induced by CO2 was detectable above natural seasonal variations.

Improved solar-driven photocatalytic performance of Ag_2CO_3/(BiO)_2CO_3 prepared in-situ

International Nuclear Information System (INIS)

Zhong, Junbo; Li, Jianzhang; Huang, Shengtian; Cheng, Chaozhu; Yuan, Wei; Li, Minjiao; Ding, Jie

2016-01-01

Highlights: • Ag_2CO_3/(BiO)_2CO_3 photocatalysts were prepared in-situ. • The photo-induced charge separation rate has been greatly increased. • The photocatalytic activity has been greatly promoted. - Abstract: Ag_2CO_3/(BiO)_2CO_3 composites have been fabricated in-situ via a facile parallel flaw co-precipitation method. The specific surface area, structure, morphology, and the separation rate of photo-induced charge pairs of the photocatalysts were characterized by Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy(DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and surface photovoltage (SPV) spectroscopy, respectively. XRD patterns and DRS demonstrated that Ag_2CO_3 has no effect on the crystal phase and bandgap of (BiO)_2CO_3. The existence of Ag_2CO_3 in the composites enhances the separation rate of photo-induced charge pairs of the photocatalysts. The photocatalytic performance of Ag_2CO_3/(BiO)_2CO_3 was evaluated by the decolorization of methyl orange (MO) aqueous solution under simulated solar irradiation. It was found that the simulated solar-induced photocatalytic activity of Ag_2CO_3/(BiO)_2CO_3 copmposites was significantly improved, which was mainly attributed to the enhanced surface area and the separation rate of photo-induced charge pairs.

Co-localisation of the Kir6.2/SUR1 channel complex with glucagon-like peptide-1 and glucose-dependent insulinotrophic polypeptide expression in human ileal cells and implications for glycaemic control in new onset type 1 diabetes

DEFF Research Database (Denmark)

Nielsen, Lotte B; Ploug, Kenneth B; Swift, Peter

2007-01-01

on glucose-sensing tissues in vivo that may affect the overall glycaemic control in children with new-onset type 1 diabetes. DESIGN AND METHODS: Western blot and immunohistochemical analyses were performed for expression and co-localisation studies. Meal-stimulated C-peptide test was carried out in 257...... children at 1, 6 and 12 months after diagnosis. Genotyping for the Glu23Lys variant was by PCR-restriction fragment length polymorphism. RESULTS: Kir6.2 and SUR1 co-localise with GLP-1 in L-cells and with GIP in K-cells in human ileum tissue. Children with type 1 diabetes carrying the hyperactive Glu23Lys...... with type 1 diabetes....

Experimental and theoretical analysis of defocused CO2 laser microchanneling on PMMA for enhanced surface finish

Science.gov (United States)

Prakash, Shashi; Kumar, Subrata

2017-02-01

The poor surface finish of CO2 laser-micromachined microchannel walls is a major limitation of its utilization despite several key advantages, like low fabrication cost and low time consumption. Defocused CO2 laser beam machining is an effective solution for fabricating smooth microchannel walls on polymer and glass substrates. In this research work, the CO2 laser microchanneling process on PMMA has been analyzed at different beam defocus positions. Defocused processing has been investigated both theoretically and experimentally, and the depth of focus and beam diameter have been determined experimentally. The effect of beam defocusing on the microchannel width, depth, surface roughness, heat affected zone and microchannel profile were examined. A previously developed analytical model for microchannel depth prediction has been improved by incorporating the threshold energy density factor. A semi-analytical model for predicting the microchannel width at different defocus positions has been developed. A semi-empirical model has also been developed for predicting microchannel widths at different defocusing conditions for lower depth values. The developed models were compared and verified by performing actual experiments. Multi-objective optimization was performed to select the best optimum set of input parameters for achieving the desired surface roughness.

Enhanced electrochemical performance of LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 by nanoscale surface modification with Co_3O_4

International Nuclear Information System (INIS)

Huang, Yaqun; Huang, Yunhui; Hu, Xianluo

2017-01-01

Highlights: • Facile coating method to prepare Co_3O_4-modified NCA. • Co_3O_4 is uniformly coated on the surface of NCA. • The nanolayer coating protects the surface of NCA during Li cycling. • Co_3O_4-modified NCA exhibits enhanced cyclability and rate capability. - Abstract: LiNi_0_._8Co_0_._1_5Al_0_._0_5O_2 (NCA) has attracted much attention because of its high capacity and low cost. Herein, we report a facile wet-chemical route to prepare a Co_3O_4-modified NCA cathode material with enhanced electrochemical performance for lithium-ion batteries. The as-prepared Co_3O_4-coated NCA cathode material delivers a specific capacity of 207.6 mAh g"−"1 with an initial Coulombic efficiency of 90.8% at 0.1 C. The capacity retention of the Co_3O_4-coated NCA cathode material is as high as 91.6% at 1 C between the potential from 2.8 to 4.3 V after 100 cycles. More importantly, the capacity retention of the resulting Co_3O_4-coated NCA is higher than 94.7% after 100 cycles at 0.2 C. In addition, the Co_3O_4-coated NCA cathode material exhibits good rate capability, especially a high discharge capacity at a high current density. The outstanding electrochemical performance of Co_3O_4-coated NCA is assigned to the surface coating of Co_3O_4 that may react with lithium-containing impurities on the surface and decrease the charge-transfer resistance.

Laser surface treatment of S235JRC carbon steel with Co{sub 2}B nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Simsek, Tuncay [Hacettepe Univ., Ankara (Turkey). Dept. of Physics Engineering; Baris, Mustafa [Eti Maden Works General Management, Ankara (Turkey). Dept. of Technology Development; Akkurt, Adnan [Gazi Univ., Ankara (Turkey). Dept. of Industrial Design Engineering

2017-06-15

In this study, Co{sub 2}B nanocrystals, which were synthesized in a planetary type mill by using the mechanochemical method, were pre-coated on the surface of S235JRC low carbon steel substrates, and then the surfaces were clad using a CO{sub 2} laser. In the experiments, laser scan speed was kept constant and laser power was specified as the variable parameter. The microstructure and phases of the coatings were investigated by using X-ray diffractometry, scanning electron microscopy, and optical microscopy. The mechanical properties of the coatings were characterized using micro-hardness, ball-on-disc wear, and scratch testing. The thickness of the coatings depending on the laser power was measured in the range 35-71 μm. The hardness and the wear resistance of the coatings were approximately 3 times higher compared to the base metal due to FeN{sub 0.0760}, Fe{sub 15.1}C, FeCo, and B{sub 2}C{sub 5}N{sub 2} phases of the coatings. The most durable coatings against wear were obtained at 174 W and 220 W laser powers.

Passive wireless surface acoustic wave sensors for monitoring sequestration sites CO₂ emission

Energy Technology Data Exchange (ETDEWEB)

Wang, Yizhong [Univ. of Pittsburgh, PA (United States); Chyu, Minking [Univ. of Pittsburgh, PA (United States); Wang, Qing-Ming [Univ. of Pittsburgh, PA (United States)

2013-02-14

University of Pittsburgh’s Transducer lab has teamed with the U.S. Department of Energy’s National Energy Technology Laboratory (DOE NETL) to conduct a comprehensive study to develop/evaluate low-cost, efficient CO₂ measuring technologies for geological sequestration sites leakage monitoring. A passive wireless CO₂ sensing system based on surface acoustic wave technology and carbon nanotube nanocomposite was developed. Surface acoustic wave device was studied to determine the optimum parameters. Delay line structure was adopted as basic sensor structure. CNT polymer nanocomposite was fabricated and tested under different temperature and strain condition for natural environment impact evaluation. Nanocomposite resistance increased for 5 times under pure strain, while the temperature dependence of resistance for CNT solely was -1375ppm/°C. The overall effect of temperature on nanocomposite resistance was -1000ppm/°C. The gas response of the nanocomposite was about 10% resistance increase under pure CO₂ . The sensor frequency change was around 300ppm for pure CO₂ . With paralyne packaging, the sensor frequency change from relative humidity of 0% to 100% at room temperature decreased from over 1000ppm to less than 100ppm. The lowest detection limit of the sensor is 1% gas concentration, with 36ppm frequency change. Wireless module was tested and showed over one foot transmission distance at preferred parallel orientation.

Solar2Fuel: XPS and TPD characterization of functionalized TiO{sub 2} surfaces for photocatalytic reduction of CO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Staier, Florian; Grunze, Michael; Zharnikov, Michael [Angewandte Physikalische Chemie, Universitaet Heidelberg, INF 253, 69120 Heidelberg (Germany)

2011-07-01

The handling of CO{sub 2} produced by industrial installations and power plants has become a very important environmental issue nowadays because of it's generally accepted impact on the green house effect. In this context, a storage of CO{sub 2} or its conversation to fuel or useful chemicals are highly desirable. Along these lines, the solar2fuel project, funded by BMBF, aims on photocatalytic conversion of CO{sub 2} to methanol with a sufficient quantum efficiency which can justify and make rentable an industrial realization of the process. As the primary catalytic system TiO{sub 2} nanoparticle powder coatings are used. These particles are doped with metals to enhance their catalytic activity and functionalized with specially designed dyes which promote photocatalytic reaction and move the absorption spectrum from UV (characteristic of TiO{sub 2}) to the visible range. We present first results on characterization of these catalytic systems by several complimentary techniques as well as on temperature-programmed-desorption of CO{sub 2} and methanol from these functionalized surfaces.

Mesoscale modelling of atmospheric CO2 across Denmark

DEFF Research Database (Denmark)

Lansø, Anne Sofie

2016-01-01

of the simulated atmospheric CO2 across Denmark was, in particular, affected by the Danish terrestrial surface exchanges and its temporal variability. This study urges all future modelling studies of air–sea CO2 to include short-term variability in pCO2. To capture the full heterogeneity of the surface exchanges......It is scientifically well-established that the increase of atmospheric CO2 affects the entire globe and will lead to higher surface temperatures. Although anthropogenic CO2is emitted straight into the atmosphere, it does not all contribute to the existing atmospheric CO2 reservoir. Approximately 29......% is taken up by the global oceans, due to under-saturation of CO2 in the surface waters, while another 33 % is taken up by the terrestrial biosphere, via photosynthesis. In order to estimate the effects of increasing anthropogenic emissions of CO2 more accurately in the future, it is essential to understand...

CO2 leakage from carbon dioxide capture and storage (CCS) systems affects organic matter cycling in surface marine sediments.

Science.gov (United States)

Rastelli, Eugenio; Corinaldesi, Cinzia; Dell'Anno, Antonio; Amaro, Teresa; Greco, Silvestro; Lo Martire, Marco; Carugati, Laura; Queirós, Ana M; Widdicombe, Stephen; Danovaro, Roberto

2016-12-01

Carbon dioxide capture and storage (CCS), involving the injection of CO 2 into the sub-seabed, is being promoted worldwide as a feasible option for reducing the anthropogenic CO 2 emissions into the atmosphere. However, the effects on the marine ecosystems of potential CO 2 leakages originating from these storage sites have only recently received scientific attention, and little information is available on the possible impacts of the resulting CO 2 -enriched seawater plumes on the surrounding benthic ecosystem. In the present study, we conducted a 20-weeks mesocosm experiment exposing coastal sediments to CO 2 -enriched seawater (at 5000 or 20,000 ppm), to test the effects on the microbial enzymatic activities responsible for the decomposition and turnover of the sedimentary organic matter in surface sediments down to 15 cm depth. Our results indicate that the exposure to high-CO 2 concentrations reduced significantly the enzymatic activities in the top 5 cm of sediments, but had no effects on subsurface sediment horizons (from 5 to 15 cm depth). In the surface sediments, both 5000 and 20,000 ppm CO 2 treatments determined a progressive decrease over time in the protein degradation (up to 80%). Conversely, the degradation rates of carbohydrates and organic phosphorous remained unaltered in the first 2 weeks, but decreased significantly (up to 50%) in the longer term when exposed at 20,000 ppm of CO 2 . Such effects were associated with a significant change in the composition of the biopolymeric carbon (due to the accumulation of proteins over time in sediments exposed to high-pCO 2 treatments), and a significant decrease (∼20-50% at 5000 and 20,000 ppm respectively) in nitrogen regeneration. We conclude that in areas immediately surrounding an active and long-lasting leak of CO 2 from CCS reservoirs, organic matter cycling would be significantly impacted in the surface sediment layers. The evidence of negligible impacts on the deeper sediments should be

Enhancing co-production of H2 and syngas via water splitting and POM on surface-modified oxygen permeable membranes

KAUST Repository

Wu, Xiao-Yu

2016-09-26

In this article, we report a detailed study on co-production of H2 and syngas on La0.9Ca0.1FeO3−δ (LCF-91) membranes via water splitting and partial oxidation of methane, respectively. A permeation model shows that the surface reaction on the sweep side is the rate limiting step for this process on a 0.9 mm-thick dense membrane at 990°C. Hence, sweep side surface modifications such as adding a porous layer and nickel catalysts were applied; the hydrogen production rate from water thermolysis is enhanced by two orders of magnitude to 0.37 μmol/cm2•s compared with the results on the unmodified membrane. At the sweep side exit, syngas (H2/CO = 2) is produced and negligible solid carbon is found. Yet near the membrane surface on the sweep side, methane can decompose into solid carbon and hydrogen at the surface, or it may be oxidized into CO and CO2, depending on the oxygen permeation flux.

Improve electrochemical performance of CeO2 surface modification LiNi0.80Co0.15Al0.05O2 cathode material

Science.gov (United States)

Xia, Shubiao; Zhang, Yingjie; Dong, Peng; Zhang, Yannan

2014-06-01

Lithium ion battery cathode material LiNi0.8Co0.15Al0.05O2 cathode has successfully prepared by co-precipitation. CeO2 surface modification has improved LiNi0.80Co0.15Al0.05O2 electrochemical performance use sol-gel method and subsequent heat treatment at 600 °C for 5 h. Different to other conventional coating material, CeO2 coating layer can not only inhibit the reaction of the electrode and the electrolyte, but also can reduce the impedance of electron transfer due to its high conductivity, and inhibit the production of Ni2+ because of its high oxidation. The surface-modified and pristine LiNi0.80Co0.15Al0.05O2 powders are characterized by XRD, SEM, TEM, XPS, CV and DSC. When CeO2 coating is 0.02% (mole ratio), contrast to pristine NCA, the CeO2-coated NCA cathode exhibits no decrease in its initial specific capacity of 184 mAh g -1 (at 0.2 C) and excellent capacity retention (86% of its initial capacity at 1 C) between 2.75 and 4.3 V after 100 cycles. The results indicate that the CeO2 surface treatment should be an effective way to improve cycle properties due to CeO2 inhibit the electrodes and the electrolyte side effects.

A Model for Interpreting High-Tower CO2 Concentration Records for the Surface Carbon Balance Information

Science.gov (United States)

Chen, B.; Chen, J. M.; Higuchi, K.; Chan, D.; Shashkov, A.

2002-05-01

Atmospheric CO2 concentration measurements have been made by scientists of Meteorological Service of Canada on a 40 m tower for the last 10 years at 15 minute intervals over a mostly intact boreal forest near Fraserdale (50N, 81W), Ontario, Canada. The long time records of CO2 as well as basic meteorological variables provide a unique opportunity to investigate any potential changes in the ecosystem in terms of carbon balance. A model is needed to decipher the carbon cycle signals from the diurnal and seasonal variation patterns in the CO2 record. For this purpose, the Boreal Ecosystem Productivity Simulator (BEPS) is expanded to include a one-dimensional CO2 vertical transfer model involving the interaction between plant canopies and the atmosphere in the surface layer and the diurnal dynamics of the mixed layer. An analytical solution of the scalar transfer equation within the surface layer is found using an assumption that the diurnal oscillation of CO2 concentration at a given height is sinusoidal, which is suitable for the investigation of the changes in diurnal variation pattern over the 10 year period. The complex interactions between the daily cycle of the atmosphere and vegetation CO2 exchange and the daily evolution of mixed layer entrainment of CO2 determines the CO2 variation pattern at a given height. The expanded BEPS can simulate within ñ2 ppm the hourly CO2 records at the 40 m measurement height. The annual totals of gross primary productivity (GPP), net primary productivity (NPP) and net ecosystem productivity (NEP), summed up from the hourly results, agree within 5% of previous estimates of BEPS at daily steps, indicating the internal consistency of the hourly model. The model is therefore ready for exploring changes in the CO2 record as affected by changes in the forest ecosystems upwind of the tower. Preliminary results indicate that the diurnal variation amplitude of CO2 has increased by 10-20% over the 10 years period, and this change can

Cu-Sn Bimetallic Catalyst for Selective Aqueous Electroreduction of CO2 to CO

KAUST Repository

Sarfraz, Saad

2016-03-23

We report a selective and stable electrocatalyst utilizing non-noble metals consisting of Cu and Sn for the efficient and selective reduction of CO2 to CO over a wide potential range. The bimetallic electrode was prepared through the electrodeposition of Sn species on the surface of oxide-derived copper (OD-Cu). The Cu surface, when decorated with an optimal amount of Sn, resulted in a Faradaic efficiency (FE) for CO greater than 90% and a current density of −1.0 mA cm−2 at −0.6 V vs. RHE, compared to the CO FE of 63% and −2.1 mA cm−2 for OD-Cu. Excess Sn on the surface caused H2 evolution with a decreased current density. X-ray diffraction (XRD) suggests the formation of Cu-Sn alloy. Auger electron spectroscopy of the sample surface exhibits zero-valent Cu and Sn after the electrodeposition step. Density functional theory (DFT) calculations show that replacing a single Cu atom with a Sn atom leaves the d-band orbitals mostly unperturbed, signifying no dramatic shifts in the bulk electronic structure. However, the Sn atom discomposes the multi-fold sites on pure Cu, disfavoring the adsorption of H and leaving the adsorption of CO relatively unperturbed. Our catalytic results along with DFT calculations indicate that the presence of Sn on reduced OD-Cu diminishes the hydrogenation capability—i.e., the selectivity towards H2 and HCOOH—while hardly affecting the CO productivity. While the pristine monometallic surfaces (both Cu and Sn) fail to selectively reduce CO2, the Cu-Sn bimetallic electrocatalyst generates a surface that inhibits adsorbed H*, resulting in improved CO FE. This study presents a strategy to provide a low-cost non-noble metals that can be utilized as a highly selective electrocatalyst for the efficient aqueous reduction of CO2.

Composites of ionic liquid and amine-modified SAPO 34 improve CO2 separation of CO2-selective polymer membranes

Science.gov (United States)

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

2017-07-01

Mixed matrix membranes with ionic liquids and molecular sieve particles had high CO2 permeabilities, but CO2 separation from small gas molecules such as H2 was dissatisfied because of bad interfacial interaction between ionic liquid and molecular sieve particles. To solve that, amine groups were introduced to modify surface of molecular sieve particles before loading with ionic liquid. SAPO 34 was adopted as the original filler, and four mixed matrix membranes with different fillers were prepared on the outer surface of ceramic hollow fibers. Both surface voids and hard agglomerations disappeared, and the surface became smooth after SAPO 34 was modified by amine groups and ionic liquid [P66614][2-Op]. Mixed matrix membranes with composites of amine-modified SAPO 34 and ionic liquid exhibited excellent CO2 permeability (408.9 Barrers) and CO2/H2 selectivity (22.1).

Seasonal and temporal CO2 dynamics in three tropical mangrove creeks - A revision of global mangrove CO2 emissions

Science.gov (United States)

Rosentreter, Judith A.; Maher, D. T.; Erler, D. V.; Murray, R.; Eyre, B. D.

2018-02-01

Continuous high-resolution surface water pCO2 and δ13C-CO2 and 222Rn (dry season only) were measured over two tidal cycles in the wet and dry season in three tropical tidal mangrove creeks on the north-eastern coast of Queensland, Australia. Mangrove surface water pCO2 followed a clear tidal pattern (ranging from 387 to 13,031 μatm) with higher pCO2-values in the wet season than in the dry season. The δ13C-CO2 in the mangrove waters ranged from -21.7 to -8.8‰ and was rather indicative of a mixed source than a distinct mangrove signature. Surface water CO2 was likely driven by a combination of mangrove and external carbon sources, e.g. exchange with groundwater/pore water enriched in 13C, or terrestrial carbon inputs with a significant contribution of C4-vegetation (sugar cane) source. The kinetic and equilibrium fractionation during the gas exchange at the water-atmosphere interface may have further caused a 13C-enrichment of the CO2 pool in the mangrove surface waters. Average CO2 evasion rates (58.7-277.6 mmol m-2 d-1) were calculated using different empirical gas transfer velocity models. Using our high-resolution time series data and previously published data, the average CO2 flux rate in mangrove ecosystems was estimated to be 56.5 ± 8.9 mmol m-2 d-1, which corresponds to a revised global mangrove CO2 emission of 34.1 ± 5.4 Tg C per year.

Optimization of foaming properties of sludge protein solution by 60Co γ-ray/H2O2 using response surface methodology

International Nuclear Information System (INIS)

Xiang, Yulin; Xiang, Yuxiu; Wang, Lipeng; Zhang, Zhifang

2016-01-01

Response surface methodology and Box-Behnken experimental design were used to model and optimize the operational parameters of foaming properties of the sludge protein solution by 60 Co γ-ray/H 2 O 2 treatment. The four variables involved in this research were the protein solution concentration, H 2 O 2 , pH and dose. In the range studied, statistical analysis of the results showed that selected variables had a significant effect on protein foaming properties. The optimized conditions contained: protein solution concentration 26.50% (v/v), H 2 O 2 concentration 0.30% (v/v), pH value 9.0, and dose 4.81 kGy. Under optimal conditions, the foamability and foam stability approached 23.3 cm and 21.3 cm, respectively. Regression analysis with R 2 value of 0.9923 (foamability) and 0.9922 (foam stability) indicated a satisfactory correlation between the experimental data and predicted values (response). In addition, based on a feasibility analysis, the 60 Co γ-ray/H 2 O 2 method can improve odor and color of the protein foaming solution. - Highlights: • Effects of 60 Co γ-ray/H 2 O 2 on foaming properties of sludge protein were studied. • Response surface methodology and Box-Behnken experimental design were applied. • 60 Co γ-ray/H 2 O 2 method can improve foaming properties of protein solution.

Surface-reconstructed Cu Electrode via a Facile Electrochemical Anodization-Reduction Process for Low Overpotential CO 2 reduction

KAUST Repository

Min, Shixiong

2017-03-21

A high-surface-area Cu electrode, fabricated by a simple electrochemical anodization-reduction method, exhibits high activity and selectivity for CO2 reduction at low overpotential in 0.1 M KHCO3 solution. A faradaic efficiency of 37% for HCOOH and 27% for CO production was achieved with the current density of 1.5 mA cm-2 at −0.64 V vs. RHE, much higher than that of polycrystalline Cu. The enhanced catalytic performance is a result of the formation of the high electrochemical active surface area and high density of preferred low-index facets.

Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298K from Quantum Mechanics Free Energy Calculations with Explicit Water.

Science.gov (United States)

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

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions are not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out Quantum Mechanics (QM) calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2RR conditions) to examine the initial reaction pathways to form CO and formate (HCOO - ) from CO 2 through free energy calculations at 298K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ- ), with a free energy barrier of ΔG ‡ =0.43 eV, the rate determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 eV and 0.30 eV, respectively. HCOO - formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO - formation occurs in the first electron transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution we need to control this first step of CO 2 binding, which might involve alloying or changing the structure at the nanoscale.

An attemp to use a pulsed CO2 laser for decontamination of radioactive metal surfaces

Directory of Open Access Journals (Sweden)

MILAN S. TRTICA

2000-06-01

Full Text Available There is a growing interest in laser radioactive decontamination of metal surfaces. It offers advantages over conventional methods: improved safety, reduction of secondary waste, reduced waste volume, acceptable cost. The main mechanism of cleaning by lasers is ablation. A pulsed TEA CO2 laser was used in this work for surface cleaning in order to show that ablation of metal surfaces is possible even at relatively low pulse energies, and to suggest that it could be competitive with other lasers because of much higher energy efficiencies. A brief theoretical analysis was made before the experiments. The laser beam was focused using a KBr-lens onto a surface contaminated with 137Cs (b-, t1/2 = 30.17 y. Three different metals were used: stainless steel, copper and aluminium. The ablated material was pumped out in an air atmosphere and transferred to a filter. The presence of activity on the filter was shown by a germanium detector-multichannel analyzer. The activity levels were measured by a GM counter. The calculated decontamination factors and collection factors showed that ablation occurs with a relatively high efficiency of decontamination. This investigation suggests that decontamination using a CO2 laser should be seriously considered.

Controls of evapotranspiration and CO2 fluxes from scots pine by surface conductance and abiotic factors.

Directory of Open Access Journals (Sweden)

Tianshan Zha

Full Text Available Evapotranspiration (E and CO2 flux (Fc in the growing season of an unusual dry year were measured continuously over a Scots pine forest in eastern Finland, by eddy covariance techniques. The aims were to gain an understanding of their biological and environmental control processes. As a result, there were obvious diurnal and seasonal changes in E, Fc , surface conductance (gc , and decoupling coefficient (Ω, showing similar trends to those in radiation (PAR and vapour pressure deficit (δ. The maximum mean daily values (24-h average for E, Fc , gc , and Ω were 1.78 mmol m(-2 s(-1, -11.18 µmol m(-2 s(-1, 6.27 mm s(-1, and 0.31, respectively, with seasonal averages of 0.71 mmol m(-2 s(-1, -4.61 µmol m(-2 s(-1, 3.3 mm s(-1, and 0.16. E and Fc were controlled by combined biological and environmental variables. There was curvilinear dependence of E on gc and Fc on gc . Among the environmental variables, PAR was the most important factor having a positive linear relationship to E and curvilinear relationship to Fc , while vapour pressure deficit was the most important environmental factor affecting gc . Water use efficiency was slightly higher in the dry season, with mean monthly values ranging from 6.67 to 7.48 μmol CO2 (mmol H2O(-1 and a seasonal average of 7.06 μmol CO2 (μmol H2O(-1. Low Ω and its close positive relationship with gc indicate that evapotranspiration was sensitive to surface conductance. Mid summer drought reduced surface conductance and decoupling coefficient, suggesting a more biotic control of evapotranspiration and a physiological acclimation to dry air. Surface conductance remained low and constant under dry condition, supporting that a constant value of surface constant can be used for modelling transpiration under drought condition.

Global Ocean Surface Water Partial Pressure of CO₂ Database: Measurements Performed During 1968-2007 (Version 2007)

Energy Technology Data Exchange (ETDEWEB)

Kozyr, Alex [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Carbon Dioxide Information Analysis Center

2008-09-30

More than 4.1 million measurements of surface water partial pressure of CO₂ obtained over the global oceans during 1968-2007 are listed in the Lamont-Doherty Earth Observatory (LDEO) database, which includes open ocean and coastal water measurements. The data assembled include only those measured by equilibrator-CO₂ analyzer systems and have been quality-controlled based on the stability of the system performance, the reliability of calibrations for CO₂ analysis, and the internal consistency of data. To allow re-examination of the data in the future, a number of measured parameters relevant to pCO₂ measurements are listed. The overall uncertainty for the pCO₂ values listed is estimated to be ± 2.5 µatm on the average. For simplicity and for ease of reference, this version is referred to as 2007, meaning that data collected through 31 December 2007 has been included. It is our intention to update this database annually. There are 37 new cruise/ship files in this update. In addition, some editing has been performed on existing files so this should be considered a V2007 file. Also we have added a column reporting the partial pressure of CO₂ in seawater in units of Pascals. The data presented in this database include the analyses of partial pressure of CO₂ (pCO₂), sea surface temperature (SST), sea surface salinity (SSS), pressure of the equilibration, and barometric pressure in the outside air from the ship’s observation system. The global pCO₂ data set is available free of charge as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center (CDIAC). The NDP consists of the oceanographic data files and this printed documentation, which describes the procedures and methods used to obtain the data.

Sur terre comme sur mer: organisations spatiales en mer du Nord et mer de Norvège

Directory of Open Access Journals (Sweden)

Maryvonne LE BERRE

1998-09-01

Full Text Available L'article montre, au moyen de représentations cartographiques et graphiques, les structures spatiales développées en mer pour l'exploitation des hydrocarbures. Malgré les différences de milieu, l'appropriation et l'occupation territoriales du domaine maritime s'effectuent selon les mêmes principes que sur le continent, à ceci près que ce qui s'étale en surface sur le continent se développe à la verticale en mer.

A rapid transition from ice covered CO2–rich waters to a biologically mediated CO2 sink in the eastern Weddell Gyre

Directory of Open Access Journals (Sweden)

W. Geibert

2008-09-01

Full Text Available Circumpolar Deep Water (CDW, locally called Warm Deep Water (WDW, enters the Weddell Gyre in the southeast, roughly at 25° E to 30° E. In December 2002 and January 2003 we studied the effect of entrainment of WDW on the fugacity of carbon dioxide (fCO2 and dissolved inorganic carbon (DIC in Weddell Sea surface waters. Ultimately the fCO2 difference across the sea surface drives air-sea fluxes of CO2. Deep CTD sections and surface transects of fCO2 were made along the Prime Meridian, a northwest-southeast section, and along 17° E to 23° E during cruise ANT XX/2 on FS Polarstern. Upward movement and entrainment of WDW into the winter mixed layer had significantly increased DIC and fCO2 below the sea ice along 0° W and 17° E to 23° E, notably in the southern Weddell Gyre. Nonetheless, the ice cover largely prevented outgassing of CO2 to the atmosphere. During and upon melting of the ice, biological activity rapidly reduced surface water fCO2 by up to 100 μatm, thus creating a sink for atmospheric CO2. Despite the tendency of the surfacing WDW to cause CO2 supersaturation, the Weddell Gyre may well be a CO2 sink on an annual basis due to this effective mechanism involving ice cover and ensuing biological fCO2 reduction. Dissolution of calcium carbonate (CaCO3 in melting sea ice may play a minor role in this rapid reduction of surface water fCO2.

An attemp to use a pulsed CO2 laser for decontamination of radioactive metal surfaces

OpenAIRE

MILAN S. TRTICA; SCEPAN S. MILJANIC; NATASA N. STJEPANOVIC

2000-01-01

There is a growing interest in laser radioactive decontamination of metal surfaces. It offers advantages over conventional methods: improved safety, reduction of secondary waste, reduced waste volume, acceptable cost. The main mechanism of cleaning by lasers is ablation. A pulsed TEA CO2 laser was used in this work for surface cleaning in order to show that ablation of metal surfaces is possible even at relatively low pulse energies, and to suggest that it could be competitive with other lase...

CO2-Induced ATP-Dependent Release of Acetylcholine on the Ventral Surface of the Medulla Oblongata.

Science.gov (United States)

Huckstepp, Robert T R; Llaudet, Enrique; Gourine, Alexander V

2016-01-01

Complex mechanisms that detect changes in brainstem parenchymal PCO2/[H+] and trigger adaptive changes in lung ventilation are responsible for central respiratory CO2 chemosensitivity. Previous studies of chemosensory signalling pathways suggest that at the level of the ventral surface of the medulla oblongata (VMS), CO2-induced changes in ventilation are (at least in part) mediated by the release and actions of ATP and/or acetylcholine (ACh). Here we performed simultaneous real-time biosensor recordings of CO2-induced ATP and ACh release from the VMS in vivo and in vitro, to test the hypothesis that central respiratory CO2 chemosensory transduction involves simultaneous recruitment of purinergic and cholinergic signalling pathways. In anaesthetised and artificially ventilated rats, an increase in inspired CO2 triggered ACh release on the VMS with a peak amplitude of ~5 μM. Release of ACh was only detected after the onset of CO2-induced activation of the respiratory activity and was markedly reduced (by ~70%) by ATP receptor blockade. In horizontal slices of the VMS, CO2-induced release of ATP was reliably detected, whereas CO2 or bath application of ATP (100 μM) failed to trigger release of ACh. These results suggest that during hypercapnia locally produced ATP induces or potentiates the release of ACh (likely from the medullary projections of distal groups of cholinergic neurones), which may also contribute to the development and/or maintenance of the ventilatory response to CO2.

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

Science.gov (United States)

Navaee, Aso; Salimi, Abdollah

2018-05-01

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

Forecasting global atmospheric CO2

International Nuclear Information System (INIS)

Agusti-Panareda, A.; Massart, S.; Boussetta, S.; Balsamo, G.; Beljaars, A.; Engelen, R.; Jones, L.; Peuch, V.H.; Chevallier, F.; Ciais, P.; Paris, J.D.; Sherlock, V.

2014-01-01

A new global atmospheric carbon dioxide (CO 2 ) real-time forecast is now available as part of the preoperational Monitoring of Atmospheric Composition and Climate - Interim Implementation (MACC-II) service using the infrastructure of the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System (IFS). One of the strengths of the CO 2 forecasting system is that the land surface, including vegetation CO 2 fluxes, is modelled online within the IFS. Other CO 2 fluxes are prescribed from inventories and from off-line statistical and physical models. The CO 2 forecast also benefits from the transport modelling from a state-of-the-art numerical weather prediction (NWP) system initialized daily with a wealth of meteorological observations. This paper describes the capability of the forecast in modelling the variability of CO 2 on different temporal and spatial scales compared to observations. The modulation of the amplitude of the CO 2 diurnal cycle by near-surface winds and boundary layer height is generally well represented in the forecast. The CO 2 forecast also has high skill in simulating day-to-day synoptic variability. In the atmospheric boundary layer, this skill is significantly enhanced by modelling the day-to-day variability of the CO 2 fluxes from vegetation compared to using equivalent monthly mean fluxes with a diurnal cycle. However, biases in the modelled CO 2 fluxes also lead to accumulating errors in the CO 2 forecast. These biases vary with season with an underestimation of the amplitude of the seasonal cycle both for the CO 2 fluxes compared to total optimized fluxes and the atmospheric CO 2 compared to observations. The largest biases in the atmospheric CO 2 forecast are found in spring, corresponding to the onset of the growing season in the Northern Hemisphere. In the future, the forecast will be re-initialized regularly with atmospheric CO 2 analyses based on the assimilation of CO 2 products retrieved from satellite

A two-dimensional hydrodynamic model of turbulent transfer of CO2 and H2O over a heterogeneous land surface

Science.gov (United States)

Mukhartova, Yu. V.; Krupenko, A. S.; Mangura, P. A.; Levashova, N. T.

2018-01-01

A two-dimensional hydrodynamic model was developed and applied to describe turbulent fluxes of CO2 and H2O within the atmospheric surface layer over a heterogeneous land surface featuring mosaic vegetation and complex topography. Numerical experiments were carried out with a 4.5-km profile that crosses a hilly region in the central part of European Russia, with the diverse land-use patterns (bare soil, crop areas, grasslands, and forests). The results showed very strong variability of the vertical and horizontal turbulent CO2 and H2O fluxes. The standard deviations of the vertical fluxes were estimated for separate profile sections with uniform vegetation cover for daylight conditions in summer, and they were comparable with the mean vertical fluxes for corresponding sections. The highest horizontal turbulent fluxes occurred at the boundaries between different plant communities and at irregularities in surface profile. In some cases, these fluxes reached 10-20% of the absolute values of the mean vertical fluxes for corresponding profile sections. Significant errors in estimating the local and integrated fluxes e.g. when using the eddy covariance technique, can result from ignoring the surface topography, even in the case of relatively large plots with uniform vegetation cover.

Nasicon-Type Surface Functional Modification in Core-Shell LiNi0.5Mn0.3Co0.2O2@NaTi2(PO4)3 Cathode Enhances Its High-Voltage Cycling Stability and Rate Capacity toward Li-Ion Batteries.

Science.gov (United States)

Liang, Longwei; Sun, Xuan; Wu, Chen; Hou, Linrui; Sun, Jinfeng; Zhang, Xiaogang; Yuan, Changzhou

2018-02-14

Surface modifications are established well as efficient methodologies to enhance comprehensive Li-storage behaviors of the cathodes and play a significant role in cutting edge innovations toward lithium-ion batteries (LIBs). Herein, we first logically devised a pilot-scale coating strategy to integrate solid-state electrolyte NaTi 2 (PO 4 ) 3 (NTP) and layered LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC) for smart construction of core-shell NMC@NTP cathodes. The Nasicon-type NTP nanoshell with exceptional ion conductivity effectively suppressed gradual encroachment and/or loss of electroactive NMC, guaranteed stable phase interfaces, and meanwhile rendered small sur-/interfacial electron/ion-diffusion resistance. By benefiting from immanently promoting contributions of the nano-NTP coating, the as-fabricated core-shell NMC@NTP architectures were competitively endowed with superior high-voltage cyclic stabilities and rate capacities within larger electrochemical window from 3.0 to 4.6 V when utilized as advanced cathodes for advanced LIBs. More meaningfully, the appealing electrode design concept proposed here will exert significant impact upon further constructing other high-voltage Ni-based cathodes for high-energy/power LIBs.

Arctic Ocean CO2 uptake: an improved multiyear estimate of the air-sea CO2 flux incorporating chlorophyll a concentrations

Science.gov (United States)

Yasunaka, Sayaka; Siswanto, Eko; Olsen, Are; Hoppema, Mario; Watanabe, Eiji; Fransson, Agneta; Chierici, Melissa; Murata, Akihiko; Lauvset, Siv K.; Wanninkhof, Rik; Takahashi, Taro; Kosugi, Naohiro; Omar, Abdirahman M.; van Heuven, Steven; Mathis, Jeremy T.

2018-03-01

We estimated monthly air-sea CO2 fluxes in the Arctic Ocean and its adjacent seas north of 60° N from 1997 to 2014. This was done by mapping partial pressure of CO2 in the surface water (pCO2w) using a self-organizing map (SOM) technique incorporating chlorophyll a concentration (Chl a), sea surface temperature, sea surface salinity, sea ice concentration, atmospheric CO2 mixing ratio, and geographical position. We applied new algorithms for extracting Chl a from satellite remote sensing reflectance with close examination of uncertainty of the obtained Chl a values. The overall relationship between pCO2w and Chl a was negative, whereas the relationship varied among seasons and regions. The addition of Chl a as a parameter in the SOM process enabled us to improve the estimate of pCO2w, particularly via better representation of its decline in spring, which resulted from biologically mediated pCO2w reduction. As a result of the inclusion of Chl a, the uncertainty in the CO2 flux estimate was reduced, with a net annual Arctic Ocean CO2 uptake of 180 ± 130 Tg C yr-1. Seasonal to interannual variation in the CO2 influx was also calculated.

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

Science.gov (United States)

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

2017-01-01

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

Effect of CO2 Laser and Fluoride Varnish Application on Microhardness of Enamel Surface Around Orthodontic Brackets.

Science.gov (United States)

Mahmoudzadeh, Majid; Rezaei-Soufi, Loghman; Farhadian, Nasrin; Jamalian, Seyed Farzad; Akbarzadeh, Mahdi; Momeni, Mohammadali; Basamtabar, Masome

2018-01-01

Introduction: Orthodontic treatment has many advantages such as esthetic improvement and self-esteem enhancement; yet it has some disadvantages such as increasing the risk of formation of white spot lesions, because it makes oral hygiene more difficult. It is rational to implement procedures to prevent these lesions. The present study was aimed to assess the effect of CO 2 laser and fluoride varnish on the surface of the enamel surface microhardness around the orthodontic braces. Methods: Eighty extracted premolar teeth were selected, scaled, polished with nonfluoridated pumic and metal brackets were bonded to them. Then, they were randomly allocated to 5 groups: control (neither fluoride nor laser is used on enamel surfaces), fluoride (4 minutes fluoride varnish treatment of the enamel surfaces), CO 2 laser (10.6 µm CO 2 laser irradiation of the teeth), laserfluoride (fluoride application after laser irradiation) and fluoride-laser (fluoride was applied and then teeth were irradiated with laser). After surface treatment around brackets on enamel, the samples were stored in 0.1% thymol for less than 5 days and then they were exposed to a 10-day microbiological caries model. Microhardness values of enamel were evaluated with Vickers test. One sample of each group (5 teeth from 80 samples) was prepared for SEM (scanning electron microscopy) and the data from 75 remaining teeth were analyzed with analysis of variance (ANOVA) and chi-square tests (α =0.05). Results: Microhardness mean values from high to low were as follow: fluoride-laser, laser-fluoride, laser, fluoride and control. Microhardness in fluoride-laser group was significantly higher compared with that of the control group. Distribution adhesive remnant index (ARI) scores were significantly different between groups and most of bond failures occurred at the enamel-adhesive interface in groups 2 to 5 and at the adhesive-bracket interface in the control group. Conclusion: Combination of fluoride varnish and

Geochemical Interaction of Middle Bakken Reservoir Rock and CO2 during CO2-Based Fracturing

Science.gov (United States)

Nicot, J. P.; Lu, J.; Mickler, P. J.; Ribeiro, L. H.; Darvari, R.

2015-12-01

This study was conducted to investigate the effects of geochemical interactions when CO2 is used to create the fractures necessary to produce hydrocarbons from low-permeability Middle Bakken sandstone. The primary objectives are to: (1) identify and understand the geochemical reactions related to CO2-based fracturing, and (2) assess potential changes of reservoir property. Three autoclave experiments were conducted at reservoir conditions exposing middle Bakken core fragments to supercritical CO2 (sc-CO2) only and to CO2-saturated synthetic brine. Ion-milled core samples were examined before and after the reaction experiments using scanning electron microscope, which enabled us to image the reaction surface in extreme details and unambiguously identify mineral dissolution and precipitation. The most significant changes in the reacted rock samples exposed to the CO2-saturated brine is dissolution of the carbonate minerals, particularly calcite which displays severely corrosion. Dolomite grains were corroded to a lesser degree. Quartz and feldspars remained intact and some pyrite framboids underwent slight dissolution. Additionally, small amount of calcite precipitation took place as indicated by numerous small calcite crystals formed at the reaction surface and in the pores. The aqueous solution composition changes confirm these petrographic observations with increase in Ca and Mg and associated minor elements and very slight increase in Fe and sulfate. When exposed to sc-CO2 only, changes observed include etching of calcite grain surface and precipitation of salt crystals (halite and anhydrite) due to evaporation of residual pore water into the sc-CO2 phase. Dolomite and feldspars remained intact and pyrite grains were slightly altered. Mercury intrusion capillary pressure tests on reacted and unreacted samples shows an increase in porosity when an aqueous phase is present but no overall porosity change caused by sc-CO2. It also suggests an increase in permeability

Optimal Surface Amino-Functionalization Following Thermo-Alkaline Treatment of Nanostructured Silica Adsorbents for Enhanced CO2 Adsorption

Directory of Open Access Journals (Sweden)

Obdulia Medina-Juárez

2016-11-01

Full Text Available Special preparation of Santa Barbara Amorphous (SBA-15, mesoporous silica with highly hexagonal ordered, these materials have been carried out for creating adsorbents exhibiting an enhanced and partially selective adsorption toward CO2. This creation starts from an adequate conditioning of the silica surface, via a thermo-alkaline treatment to increase the population of silanol species on it. CO2 adsorption is only reasonably achieved when the SiO2 surface becomes aminated after put in contact with a solution of an amino alkoxide compound in the right solvent. Unfunctionalized and amine-functionalized substrates were characterized through X-ray diffraction, N2 sorption, Raman spectroscopy, electron microscopy, 29Si solid-state Nuclear Magnetic Resonance (NMR, and NH3 thermal programmed desorption. These analyses proved that the thermo-alkaline procedure desilicates the substrate and eliminates the micropores (without affecting the SBA-15 capillaries, present in the original solid. NMR analysis confirms that the hydroxylated solid anchors more amino functionalizing molecules than the unhydroxylated material. The SBA-15 sample subjected to hydroxylation and amino-functionalization displays a high enthalpy of interaction, a reason why this solid is suitable for a strong deposition of CO2 but with the possibility of observing a low-pressure hysteresis phenomenon. Contrastingly, CH4 adsorption on amino-functionalized, hydroxylated SBA-15 substrates becomes almost five times lower than the CO2 one, thus giving proof of their selectivity toward CO2. Although the amount of retained CO2 is not yet similar to or higher than those determined in other investigations, the methodology herein described is still susceptible to optimization.

Process-based approach for the detection of CO2 injectate leakage

Science.gov (United States)

Romanak, Katherine; Bennett, Philip C.

2017-11-14

The present invention includes a method for distinguishing between a natural source of deep gas and gas leaking from a CO.sub.2 storage reservoir at a near surface formation comprising: obtaining one or more surface or near surface geological samples; measuring a CO.sub.2, an O.sub.2, a CH.sub.4, and an N.sub.2 level from the surface or near surface geological sample; determining the water vapor content at or above the surface or near surface geological samples; normalizing the gas mixture of the CO.sub.2, the O.sub.2, the CH.sub.4, the N.sub.2 and the water vapor content to 100% by volume or 1 atmospheric total pressure; determining: a ratio of CO.sub.2 versus N.sub.2; and a ratio of CO.sub.2 to N.sub.2, wherein if the ratio is greater than that produced by a natural source of deep gas CO.sub.2 or deep gas methane oxidizing to CO.sub.2, the ratio is indicative of gas leaking from a CO.sub.2 storage reservoir.

Ikaite crystals in melting sea ice - implications for pCO2 and pH levels in Arctic surface waters

Science.gov (United States)

Rysgaard, S.; Glud, R. N.; Lennert, K.; Cooper, M.; Halden, N.; Leakey, R. J. G.; Hawthorne, F. C.; Barber, D.

2012-08-01

A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (a polymorph of CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here, we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from a melting 1.7 km2 (0.5-1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice floe thickness by 0.2 m per week and resulted in an estimated 3.8 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air-sea CO2 uptake of 10.6 mmol m-2 sea ice d-1 or to 3.3 ton km-2 ice floe week-1. This is markedly higher than the estimated primary production within the ice floe of 0.3-1.3 mmol m-2 sea ice d-1. Finally, the presence of ikaite in sea ice and the dissolution of the mineral during melting of the sea ice and mixing of the melt water into the surface oceanic mixed layer accounted for half of the estimated pCO2 uptake.

Driving CO2 to a Quasi-Condensed Phase at the Interface between a Nanoparticle Surface and a Metal-Organic Framework at 1 bar and 298 K.

Science.gov (United States)

Lee, Hiang Kwee; Lee, Yih Hong; Morabito, Joseph V; Liu, Yejing; Koh, Charlynn Sher Lin; Phang, In Yee; Pedireddy, Srikanth; Han, Xuemei; Chou, Lien-Yang; Tsung, Chia-Kuang; Ling, Xing Yi

2017-08-23

We demonstrate a molecular-level observation of driving CO 2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO 2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO 2 is observed at the interface. The high surface concentration leads CO 2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO 2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO 2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>10 5 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO 2 conversion and ambient solid-gas operation.

Surface monitoring of microseismicity at the Decatur, Illinois, CO2 sequestration demonstration site

Science.gov (United States)

Kaven, Joern; Hickman, Stephen H.; McGarr, Arthur F.; Ellsworth, William L.

2015-01-01

Sequestration of CO2 into subsurface reservoirs can play an important role in limiting future emission of CO2 into the atmosphere (e.g., Benson and Cole, 2008). For geologic sequestration to become a viable option to reduce greenhouse gas emissions, large-volume injection of supercritical CO2 into deep sedimentary formations is required. These formations offer large pore volumes and good pore connectivity and are abundant (Bachu, 2003; U.S. Geological Survey Geologic Carbon Dioxide Storage Resources Assessment Team, 2013). However, hazards associated with injection of CO2 into deep formations require evaluation before widespread sequestration can be adopted safely (Zoback and Gorelick, 2012). One of these hazards is the potential to induce seismicity on pre-existing faults or fractures. If these faults or fractures are large and critically stressed, seismic events can occur with magnitudes large enough to pose a hazard to surface installations and, possibly more critical, the seal integrity of the cap rock. The Decatur, Illinois, carbon capture and storage (CCS) demonstration site is the first, and to date, only CCS project in the United States that injects a large volume of supercritical CO2 into a regionally extensive, undisturbed saline formation. The first phase of the Decatur CCS project was completed in November 2014 after injecting a million metric tons of supercritical CO2 over three years. This phase was led by the Illinois State Geological Survey (ISGS) and included seismic monitoring using deep borehole sensors, with a few sensors installed within the injection horizon. Although the deep borehole network provides a more comprehensive seismic catalog than is presented in this paper, these deep data are not publically available. We contend that for monitoring induced microseismicity as a possible seismic hazard and to elucidate the general patterns of microseismicity, the U.S. Geological Survey (USGS) surface and shallow borehole network described below

Three C-terminal residues from the sulphonylurea receptor contribute to the functional coupling between the KATP channel subunits SUR2A and Kir6.2

Science.gov (United States)

Dupuis, Julien P; Revilloud, Jean; Moreau, Christophe J; Vivaudou, Michel

2008-01-01

Cardiac ATP-sensitive potassium (KATP) channels are metabolic sensors formed by the association of the inward rectifier potassium channel Kir6.2 and the sulphonylurea receptor SUR2A. SUR2A adjusts channel gating as a function of intracellular ATP and ADP and is the target of pharmaceutical openers and blockers which, respectively, up- and down-regulate Kir6.2. In an effort to understand how effector binding to SUR2A translates into Kir6.2 gating modulation, we examined the role of a 65-residue SUR2A fragment linking transmembrane domain TMD2 and nucleotide-binding domain NBD2 that has been shown to interact with Kir6.2. This fragment of SUR2A was replaced by the equivalent residues of its close homologue, the multidrug resistance protein MRP1. The chimeric construct was expressed in Xenopus oocytes and characterized using the patch-clamp technique. We found that activation by MgADP and synthetic openers was greatly attenuated although apparent affinities were unchanged. Further chimeragenetic and mutagenetic studies showed that mutation of three residues, E1305, I1310 and L1313 (rat numbering), was sufficient to confer this defective phenotype. The same mutations had no effects on channel block by the sulphonylurea glibenclamide or by ATP, suggesting a role for these residues in activatory – but not inhibitory – transduction processes. These results indicate that, within the KATP channel complex, the proximal C-terminal of SUR2A is a critical link between ligand binding to SUR2A and Kir6.2 up-regulation. PMID:18450778

Le cuivre sur les surfaces en milieux de santé pour lutter contre les infections nosocomiales

OpenAIRE

Masson , Julien-Luc

2015-01-01

Non disponible / Not available; Les infections nosocomiales sont devenues un enjeu de Santé Publiqueprimordial. Les antibiotiques et les mesures d’hygiène deviennent insuffisantspour éradiquer ces infections.D’autres méthodes doivent être mises en oeuvre afin de permettre unemeilleure prévention. Parmi celles-ci, nous pouvons agir sur la diminution durisque de contact aux microorganismes.Au niveau des surfaces environnementales, il faudrait un matériau deremplacement à ceux utilisés habituell...

Termites as a factor of spatial differentiation of CO2 fluxes from the soils of monsoon tropical forests in Southern Vietnam

Science.gov (United States)

Lopes de Gerenyu, Valentin; Anichkin, Alexander

2016-04-01

Termites play the key role in biogeochemical transformation of organic matter acting as "moderators" of fluxes of carbon and other nutrients. They destroy not only leave litter but also coarse woody debris. Termites translocate considerable masses of dead organic materials into their houses, which leads to significant accumulations of organic matter in termite mounds. We studied the impact of termite mounds on redistribution of CO2 fluxes from soils in semi-deciduous monsoon tropical forests of southern Vietnam. Field study was performed in the Cat Tien National Park (11°21'-11°48'N, 107°10'-107°34'E). The spatial and temporary dynamics of CO2 fluxes from soils (Andosols) populated by termites were studied in plain lagerstroemia (Lagerstroemia calyculata Kurz) monsoon tropical forests. The rate of CO2 emission from the soil surface was measured by closed chamber method two-three times per month from November 2010 to December 2011. Permanent cylindrical PVC chambers (9 cm in diameter and 15 cm in height) were installed beyond the areas occupied by termite mounds (5 replications). Litter was not removed from the soil surface before the measurements. To estimate the spatial heterogeneity of the CO2 emission fluxes from soils populated by termites, a special 'termite' plot (TerPl) was equipped. It was 10×10 m in size and included three termite mounds: one mound built up by Globitermes sulphureus and two mounds populated by termites of the Odontotermes genus. Overall, 52 PVC chambers were installed permanently on the 'termite' plot (ca. 1 m apart from one another). The CO2 emission rate from TerPl was also measured by chamber closed method once in the dry season (April) and twice through the wet season (July and August). The average rate of CO2 emission from termite mounds was two times higher than that from the surrounding area (SurAr). In the dry season, it comprised 91±7 mg C/m2/h from the surrounding soils and 196±16 mg C/m2/h from the termite mounds. In the

The concurrent use of novel soil surface microclimate measurements to evaluate CO2 pulses in biocrusted interspaces in a cool desert ecosystem

Science.gov (United States)

Tucker, Colin; McHugh, Theresa A.; Howell, Armin; Gill, Richard; Weber, Bettina; Belnap, Jayne; Grote, Ed; Reed, Sasha C.

2017-01-01

Carbon cycling associated with biological soil crusts, which occupy interspaces between vascular plants in drylands globally, may be an important part of the coupled climate-carbon cycle of the Earth system. A major challenge to understanding CO2 fluxes in these systems is that much of the biotic and biogeochemical activity occurs in the upper few mm of the soil surface layer (i.e., the ‘mantle of fertility’), which exhibits highly dynamic and difficult to measure temperature and moisture fluctuations. Here, we report a multi-sensor approach to simultaneously measuring temperature and moisture of this biocrust surface layer (0–2 mm), and the deeper soil profile, concurrent with automated measurement of surface soil CO2effluxes. Our results illuminate robust relationships between biocrust water content and field CO2 pulses that have previously been difficult to detect and explain. All observed CO2 pulses over the measurement period corresponded to surface wetting events, including when the wetting events did not penetrate into the soil below the biocrust layer (0–2 mm). The variability of temperature and moisture of the biocrust surface layer was much greater than even in the 0–5 cm layer of the soil beneath the biocrust, or deeper in the soil profile. We therefore suggest that coupling surface measurements of biocrust moisture and temperature to automated CO2flux measurements may greatly improve our understanding of the climatic sensitivity of carbon cycling in biocrusted interspaces in our study region, and that this method may be globally relevant and applicable.

Surface science models of CoMoS hydrodesulfurisation catalysts

Energy Technology Data Exchange (ETDEWEB)

De Jong, A.M.; De Beer, V.H.J.; Van Veen, J.A.R.; Niemantsverdriet, J.W. [Schuit Institute of Catalysis, Eindhoven University of Technology, Eindhoven (Netherlands)

1997-07-01

Characterization of supported catalysts with surface spectroscopic techniques is often limited due to restraints imposed by the support material. The use of flat conducting substrates as a model support offers a way to apply these techniques to their full potential. Such surface science models of silica and alumina supported CoMoS catalysts have been made by impregnating thin SiO{sub 2} and Al{sub 2}O{sub 3} films with a solution of nitrilotriacetic acid (NTA) complexes of cobalt and molybdenum. X-ray Photoelectron Spectroscopy (XPS) spectra indicate that the order in which cobalt and molybdenum transfer to the sulfided state is reversed with respect to oxidic Co and Mo systems prepared by conventional methods, implying that NTA complexation retards the sulfidation of cobalt to temperatures where MoS{sub 2} is already formed. Catalytic tests show that the CoMoS model catalysts exhibit activities for thiophene desulfurisation and product distributions similar to those of their high surface area counterparts. 25 refs.

Effect of surface-breakdown plasma on metal drilling by pulsed CO2-laser radiation

Science.gov (United States)

Arutiunian, P. V.; Baranov, V. Iu.; Bobkov, I. V.; Bol'Shakov, L. A.; Dolgov, V. A.

1988-03-01

The effect of low-threshold surface breakdown produced by short (5-microsec) CO2-laser pulses on the metal drilling process is investigated. Data on the interaction of metals with laser pulses having the same duration but different shape are shown to be different. The effect of the ambient atmospheric pressure on the laser drilling process is investigated.

The Li–CO2 battery: a novel method for CO2 capture and utilization

KAUST Repository

Xu, Shaomao

2013-01-01

We report a novel primary Li-CO2 battery that consumes pure CO2 gas as its cathode. The battery exhibits a high discharge capacity of around 2500 mA h g-1 at moderate temperatures. At 100 °C the discharge capacity is close to 1000% higher than that at 40 °C, and the temperature dependence is significantly weaker for higher surface area carbon cathodes. Ex-situ FTIR and XRD analyses convincingly show that lithium carbonate (Li2CO3) is the main component of the discharge product. The feasibility of similar primary metal-CO2 batteries based on earth abundant metal anodes, such as Al and Mg, is demonstrated. The metal-CO2 battery platform provides a novel approach for simultaneous capturing of CO2 emissions and producing electrical energy. © 2013 The Royal Society of Chemistry.

Receding and advancing (CO_2 + brine + quartz) contact angles as a function of pressure, temperature, surface roughness, salt type and salinity

International Nuclear Information System (INIS)

Al-Yaseri, Ahmed Z.; Lebedev, Maxim; Barifcani, Ahmed; Iglauer, Stefan

2016-01-01

Highlights: • (Water + CO_2) contact angle on quartz increases substantially with pressure and salinity. • (Water + CO_2) contact angle on quartz increases slightly with temperature. • Surface roughness has only a minor influence on (water + CO_2 + quartz) contact angles. - Abstract: The wetting characteristics of CO_2 in rock are of vital importance in carbon geo-storage as they determine fluid dynamics and storage capacities. However, the current literature data has a high uncertainty, which translates into uncertain predictions in terms of containment security and economic project feasibility. We thus measured contact angles for the CO_2/water/quartz system at relevant reservoir conditions, and analysed the effects of pressure (0.1 to 20) MPa, temperature (296 to 343) K, surface roughness (56 to 1300) nm, salt type (NaCl, CaCl_2, and MgCl_2) and brine salinities (0 to 35) wt%. Water contact angles decreased with surface roughness, but increased with pressure, temperature, and brine salinity. Overall the contact angles were significantly increased at storage conditions (∼50°) when compared to ambient conditions (always 0°). Consequently quartz is weakly water-wet (not completely water-wet) at storage conditions, and structural and residual trapping capacities are reduced accordingly.

Estimation of the reactive mineral surface area during CO2-rich fluid-rock interaction: the influence of neogenic phases

Science.gov (United States)

Scislewski, A.; Zuddas, P.

2010-12-01

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. It is however, difficult to estimate and well normalize bulk reaction rates if the mineral surface area exposed to the aqueous solution and effectively participating on the reactions is unknown. We evaluated the changing of the reactive mineral surface area during the interaction between CO2-rich fluids and Albitite/Granitoid rocks (similar mineralogy but different abundances), reacting under flow-through conditions. Our methodology, adopting an inverse modeling approach, is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reactions by the reconstruction the chemical evolution of the interacting fluids. The irreversible mass-transfer processes is defined by a fractional degree of advancement, while calculations were carried out for Albite, Microcline, Biotite and Calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. Irrespective of the mineral abundance in granite and albitite, we found that mineral dissolution rates did not change significantly in the investigated range of time where output solution’s pH remained in the range between 6 and 8, indicating that the observed variation in fluid composition depends not on pH but rather on the variation of the parent mineral’s reactive surface area. We found that the reactive surface area of Albite varied by more than 2 orders of magnitude, while Microcline, Calcite and Biotite surface areas changed by 1-2 orders of magnitude. We propose that parent mineral chemical heterogeneity and, particularly, the stability of secondary mineral phases may explain the observed variation of the reactive surface area of the minerals. Formation of coatings at the dissolving parent mineral surfaces significantly reduced the amount of surface available to react

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

Science.gov (United States)

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.

CO oxidation on PdO surfaces

DEFF Research Database (Denmark)

Hirvi, Janne T.; Kinnunen, Toni-Jani J.; Suvanto, Mika

2010-01-01

Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable...... oxidation via the Langmuir–Hinshelwood mechanism. The reaction with a surface oxygen atom has an activation energy of 0.66 eV, which is comparable to the lowest activation energies observed on metallic surfaces. However, the reaction rate may be limited by the coverage of molecular oxygen. Actually...... adsorption, following the Eley–Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)–O surface...

The Abundance of Atmospheric CO{sub 2} in Ocean Exoplanets: a Novel CO{sub 2} Deposition Mechanism

Energy Technology Data Exchange (ETDEWEB)

Levi, A.; Sasselov, D. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Podolak, M., E-mail: amitlevi.planetphys@gmail.com [Dept. of Geosciences, Tel Aviv University, Tel Aviv, 69978 (Israel)

2017-03-20

We consider super-Earth sized planets which have a water mass fraction large enough to form an external mantle composed of high-pressure water-ice polymorphs and also lack a substantial H/He atmosphere. We consider such planets in their habitable zone, so that their outermost condensed mantle is a global, deep, liquid ocean. For these ocean planets, we investigate potential internal reservoirs of CO{sub 2}, the amount of CO{sub 2} dissolved in the ocean for the various saturation conditions encountered, and the ocean-atmosphere exchange flux of CO{sub 2}. We find that, in a steady state, the abundance of CO{sub 2} in the atmosphere has two possible states. When wind-driven circulation is the dominant CO{sub 2} exchange mechanism, an atmosphere of tens of bars of CO{sub 2} results, where the exact value depends on the subtropical ocean surface temperature and the deep ocean temperature. When sea-ice formation, acting on these planets as a CO{sub 2} deposition mechanism, is the dominant exchange mechanism, an atmosphere of a few bars of CO{sub 2} is established. The exact value depends on the subpolar surface temperature. Our results suggest the possibility of a negative feedback mechanism, unique to water planets, where a reduction in the subpolar temperature drives more CO{sub 2} into the atmosphere to increase the greenhouse effect.

Reactivity of micas and cap-rock in wet supercritical CO_2 with SO_2 and O_2 at CO_2 storage conditions

International Nuclear Information System (INIS)

Pearce, Julie K.; Dawson, Grant K.W.; Law, Alison C.K.; Biddle, Dean; Golding, Suzanne D.

2016-01-01

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO_2, O_2, and NOx, may be present in CO_2 streams from coal combustion sources. SO_2 and O_2 have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO_2 fluid may also come into contact with the base of cap-rock after CO_2 injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation. The first observation of mineral dissolution and precipitation on phyllosilicates and CO_2 storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO_2 reactions with industrial impurities SO_2 and O_2 at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO_2 containing SO_2, or SO_2 and O_2, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO_2 dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO_2 containing SO_2 or in pure supercritical CO_2. In the presence of SO_2, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was

Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

International Nuclear Information System (INIS)

Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

2017-01-01

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

KAUST Repository

Al-Sabban, Bedour

2017-05-02

Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests

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

Science.gov (United States)

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.

Surface-protected LiCoO2 with ultrathin solid oxide electrolyte film for high-voltage lithium ion batteries and lithium polymer batteries

Science.gov (United States)

Yang, Qi; Huang, Jie; Li, Yejing; Wang, Yi; Qiu, Jiliang; Zhang, Jienan; Yu, Huigen; Yu, Xiqian; Li, Hong; Chen, Liquan

2018-06-01

Surface modification of LiCoO2 with the ultrathin film of solid state electrolyte of Li1.4Al0.4Ti1.6(PO4)3 (LATP) has been realized by a new and facile solution-based method. The coated LiCoO2 reveals enhanced structural and electrochemical stability at high voltage (4.5 V vs Li+/Li) in half-cell with liquid electrolyte. Transmission electron microscopy (TEM) images show that a dense LATP coating layer is covered on the surface of LiCoO2 uniformly with thickness of less than 20 nm. The LATP coating layer is proven to be able to prevent the direct contact between the cathode and the electrolyte effectively and thus to suppress the side reactions of liquid electrolyte with LiCoO2 surface at high charging voltage. As a result, dissolution of Co3+ has been largely suppressed over prolonged cycling as indicated by the X-ray photoelectron spectroscopy (XPS) measurements. Due to this surface passivating feature, the electrochemical performance of 0.5 wt% LATP modified LiCoO2 has also been evaluated in an all solid lithium battery with poly(ethylene oxide)-based polymer electrolyte. The cell exhibits 93% discharge capacity retention of the initial discharge capacity after 50 cycles at the charging cut-off voltage of 4.2 V, suggesting that the LATP coating layer is effective to suppress the oxidation of PEO at high voltage.

Adsorption-Driven Surface Segregation of the Less Reactive Alloy Component

DEFF Research Database (Denmark)

Andersson, Klas Jerker; Calle Vallejo, Federico; Rossmeisl, Jan

2009-01-01

Counterintuitive to expectations and all prior observations of adsorbate-induced surface segregation of the more reactive alloy component (the one forming the stronger bond with the adsorbate), we show that CO adsorption at elevated pressures and temperatures pulls the less reactive Cu to the sur......Counterintuitive to expectations and all prior observations of adsorbate-induced surface segregation of the more reactive alloy component (the one forming the stronger bond with the adsorbate), we show that CO adsorption at elevated pressures and temperatures pulls the less reactive Cu...... to the surface of a CuPt near-surface alloy. The Cu surface segregation is driven by the formation of a stable self-organized CO/CuPt surface alloy structure and is rationalized in terms of the radically stronger Pt−CO bond when Cu is present in the first surface layer of Pt. The results, which are expected...

Assessing systematic errors in GOSAT CO2 retrievals by comparing assimilated fields to independent CO2 data

Science.gov (United States)

Baker, D. F.; Oda, T.; O'Dell, C.; Wunch, D.; Jacobson, A. R.; Yoshida, Y.; Partners, T.

2012-12-01

Measurements of column CO2 concentration from space are now being taken at a spatial and temporal density that permits regional CO2 sources and sinks to be estimated. Systematic errors in the satellite retrievals must be minimized for these estimates to be useful, however. CO2 retrievals from the TANSO instrument aboard the GOSAT satellite are compared to similar column retrievals from the Total Carbon Column Observing Network (TCCON) as the primary method of validation; while this is a powerful approach, it can only be done for overflights of 10-20 locations and has not, for example, permitted validation of GOSAT data over the oceans or deserts. Here we present a complementary approach that uses a global atmospheric transport model and flux inversion method to compare different types of CO2 measurements (GOSAT, TCCON, surface in situ, and aircraft) at different locations, at the cost of added transport error. The measurements from any single type of data are used in a variational carbon data assimilation method to optimize surface CO2 fluxes (with a CarbonTracker prior), then the corresponding optimized CO2 concentration fields are compared to those data types not inverted, using the appropriate vertical weighting. With this approach, we find that GOSAT column CO2 retrievals from the ACOS project (version 2.9 and 2.10) contain systematic errors that make the modeled fit to the independent data worse. However, we find that the differences between the GOSAT data and our prior model are correlated with certain physical variables (aerosol amount, surface albedo, correction to total column mass) that are likely driving errors in the retrievals, independent of CO2 concentration. If we correct the GOSAT data using a fit to these variables, then we find the GOSAT data to improve the fit to independent CO2 data, which suggests that the useful information in the measurements outweighs the negative impact of the remaining systematic errors. With this assurance, we compare

History Matching and Parameter Estimation of Surface Deformation Data for a CO2 Sequestration Field Project Using Ensemble-Based Algorithms

Science.gov (United States)

Tavakoli, Reza; Srinivasan, Sanjay; Wheeler, Mary

2015-04-01

The application of ensemble-based algorithms for history matching reservoir models has been steadily increasing over the past decade. However, the majority of implementations in the reservoir engineering have dealt only with production history matching. During geologic sequestration, the injection of large quantities of CO2 into the subsurface may alter the stress/strain field which in turn can lead to surface uplift or subsidence. Therefore, it is essential to couple multiphase flow and geomechanical response in order to predict and quantify the uncertainty of CO2 plume movement for long-term, large-scale CO2 sequestration projects. In this work, we simulate and estimate the properties of a reservoir that is being used to store CO2 as part of the In Salah Capture and Storage project in Algeria. The CO2 is separated from produced natural gas and is re-injected into downdip aquifer portion of the field from three long horizontal wells. The field observation data includes ground surface deformations (uplift) measured using satellite-based radar (InSAR), injection well locations and CO2 injection rate histories provided by the operators. We implement variations of ensemble Kalman filter and ensemble smoother algorithms for assimilating both injection rate data as well as geomechanical observations (surface uplift) into reservoir model. The preliminary estimation results of horizontal permeability and material properties such as Young Modulus and Poisson Ratio are consistent with available measurements and previous studies in this field. Moreover, the existence of high-permeability channels (fractures) within the reservoir; especially in the regions around the injection wells are confirmed. This estimation results can be used to accurately and efficiently predict and quantify the uncertainty in the movement of CO2 plume.

History matching and parameter estimation of surface deformation data for a CO2 sequestration field project using ensemble-based algorithm

Science.gov (United States)

Ping, J.; Tavakoli, R.; Min, B.; Srinivasan, S.; Wheeler, M. F.

2015-12-01

Optimal management of subsurface processes requires the characterization of the uncertainty in reservoir description and reservoir performance prediction. The application of ensemble-based algorithms for history matching reservoir models has been steadily increasing over the past decade. However, the majority of implementations in the reservoir engineering have dealt only with production history matching. During geologic sequestration, the injection of large quantities of CO2 into the subsurface may alter the stress/strain field which in turn can lead to surface uplift or subsidence. Therefore, it is essential to couple multiphase flow and geomechanical response in order to predict and quantify the uncertainty of CO2 plume movement for long-term, large-scale CO2 sequestration projects. In this work, we simulate and estimate the properties of a reservoir that is being used to store CO2 as part of the In Salah Capture and Storage project in Algeria. The CO2 is separated from produced natural gas and is re-injected into downdip aquifer portion of the field from three long horizontal wells. The field observation data includes ground surface deformations (uplift) measured using satellite-based radar (InSAR), injection well locations and CO2 injection rate histories provided by the operators. We implement ensemble-based algorithms for assimilating both injection rate data as well as geomechanical observations (surface uplift) into reservoir model. The preliminary estimation results of horizontal permeability and material properties such as Young Modulus and Poisson Ratio are consistent with available measurements and previous studies in this field. Moreover, the existence of high-permeability channels/fractures within the reservoir; especially in the regions around the injection wells are confirmed. This estimation results can be used to accurately and efficiently predict and monitor the movement of CO2 plume.

Surface modification of the titanium implant using TEA CO2 laser pulses in controllable gas atmospheres - Comparative study

International Nuclear Information System (INIS)

Ciganovic, J.; Stasic, J.; Gakovic, B.; Momcilovic, M.; Milovanovic, D.; Bokorov, M.; Trtica, M.

2012-01-01

Interaction of a TEA CO 2 laser, operating at 10.6 μm wavelength and pulse duration of 100 ns (FWHM), with a titanium implant in various gas atmospheres was studied. The Ti implant surface modification was typically studied at the moderate laser beam energy density/fluence of 28 J/cm 2 in the surrounding of air, N 2 , O 2 or He. The energy absorbed from the TEA CO 2 laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following titanium implant surface changes and phenomena were observed, depending on the gas used: (i) creation of cone-like surface structures in the atmospheres of air, N 2 and O 2 , and dominant micro-holes/pores in He ambient; (ii) hydrodynamic features, most prominent in air; (iii) formation of titanium nitride and titanium oxide layers, and (iv) occurrence of plasma in front of the implant. It can be concluded from this study that the reported laser fluence and gas ambiences can effectively be applied for enhancing the titanium implant roughness and creation of titanium oxides and nitrides on the strictly localized surface area. The appearance of plasma in front of the implants indicates relatively high temperatures created above the surface. This offers a sterilizing effect, facilitating contaminant-free conditions.

CO2 dispersion modelling over Paris region within the CO2-MEGAPARIS project

Directory of Open Access Journals (Sweden)

C. Lac

2013-05-01

Full Text Available Accurate simulation of the spatial and temporal variability of tracer mixing ratios over urban areas is a challenging and interesting task needed to be performed in order to utilise CO2 measurements in an atmospheric inverse framework and to better estimate regional CO2 fluxes. This study investigates the ability of a high-resolution model to simulate meteorological and CO2 fields around Paris agglomeration during the March field campaign of the CO2-MEGAPARIS project. The mesoscale atmospheric model Meso-NH, running at 2 km horizontal resolution, is coupled with the Town Energy Balance (TEB urban canopy scheme and with the Interactions between Soil, Biosphere and Atmosphere CO2-reactive (ISBA-A-gs surface scheme, allowing a full interaction of CO2 modelling between the surface and the atmosphere. Statistical scores show a good representation of the urban heat island (UHI with stronger urban–rural contrasts on temperature at night than during the day by up to 7 °C. Boundary layer heights (BLH have been evaluated on urban, suburban and rural sites during the campaign, and also on a suburban site over 1 yr. The diurnal cycles of the BLH are well captured, especially the onset time of the BLH increase and its growth rate in the morning, which are essential for tall tower CO2 observatories. The main discrepancy is a small negative bias over urban and suburban sites during nighttime (respectively 45 m and 5 m, leading to a few overestimations of nocturnal CO2 mixing ratios at suburban sites and a bias of +5 ppm. The diurnal CO2 cycle is generally well captured for all the sites. At the Eiffel tower, the observed spikes of CO2 maxima occur every morning exactly at the time at which the atmospheric boundary layer (ABL growth reaches the measurement height. At suburban ground stations, CO2 measurements exhibit maxima at the beginning and at the end of each night, when the ABL is fully contracted, with a strong spatio-temporal variability. A

Ikaite crystals in melting sea ice – implications for pCO2 and pH levels in Arctic surface waters

Directory of Open Access Journals (Sweden)

R. J. G. Leakey

2012-08-01

Full Text Available A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air–sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (a polymorph of CaCO3·6H2O in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here, we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from a melting 1.7 km2 (0.5–1 m thick drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice floe thickness by 0.2 m per week and resulted in an estimated 3.8 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air–sea CO2 uptake of 10.6 mmol m−2 sea ice d−1 or to 3.3 ton km−2 ice floe week−1. This is markedly higher than the estimated primary production within the ice floe of 0.3–1.3 mmol m−2 sea ice d−1. Finally, the presence of ikaite in sea ice and the dissolution of the mineral during melting of the sea ice and mixing of the melt water into the surface oceanic mixed layer accounted for half of the estimated pCO2 uptake.

XPS and surface resistivity measurements of plasma - treated FEP co-polymer

International Nuclear Information System (INIS)

Pitrus, R.K.; Brack, N.; Liesegang, J.; Pigram, P.J.

2002-01-01

Full text: Fluorinated polymers such as fluorinated ethylene propylene (FEP) and poly(tetrafluoroethylene) (PTFE) play an important role in many applications due to their many desirable properties such as chemical resistivity, inertness, electrical stability and low dielectric constant; however, one disadvantage of fluorinated polymers is their extreme surface hydrophobicity. Previous studies show that plasma treatment will modify the surface by increasing the surface free energy and also offer a rapid and convenient method for pre-treating the polymers for many purposes. This paper, through resistivity and XPS (x-ray photoelectron spectroscopy) measurements, attempts to discover basic effects of such plasma treatment. Fluorinated ethylene propylene (FEP) co-polymer film of (0.05) mm thickness (obtained commercially) and with the following structure (CF 2 -CF 2 )-(CF(CF 3 )CF 2 )- was used. A suitable cleaning procedure was used to remove adventitious carbon from the surface. XPS has been used to study FEP film properties. The spectra of XPS were analyzed with the main focus on carbon and fluorine as they compose the elemental component of FEP film. A value of 2.05 was obtained for the F/C ratio, which is slightly higher than the theoretical F/C value estimated from the chemical structure of FEP (F/C 2). The clean film was then air plasma treated (pressure 10 -1 torr and power 30W) for various treatment times to produce a higher energy fluoropolymer surface. XPS studies investigated changes to the polymer surface and determined that oxidation occurs on the FEP surface. The oxidation reactions on the FEP surface form oxygen functional groups such as C-O and C=O groups. The results also show that the percentage of CF 2 and CF 3 in the co-polymer surface decreased with exposure time and the percentage of CF, C-C, C-O and C=O increased. There is a sharp decrease in F/C ratio and increase in O/C ratio. In addition to XPS, the resistivity of FEP-film was measured by a

CO2 clearance by membrane lungs.

Science.gov (United States)

Sun, Liqun; Kaesler, Andreas; Fernando, Piyumindri; Thompson, Alex J; Toomasian, John M; Bartlett, Robert H

2018-05-01

Commercial membrane lungs are designed to transfer a specific amount of oxygen per unit of venous blood flow. Membrane lungs are much more efficient at removing CO 2 than adding oxygen, but the range of CO 2 transfer is rarely reported. Commercial membrane lungs were studied with the goal of evaluating CO 2 removal capacity. CO 2 removal was measured in 4 commercial membrane lungs under standardized conditions. CO 2 clearance can be greater than 4 times that of oxygen at a given blood flow when the gas to blood flow ratio is elevated to 4:1 or 8:1. The CO 2 clearance was less dependent on surface area and configuration than oxygen transfer. Any ECMO system can be used for selective CO 2 removal.

Explicit correlation treatment of the potential energy surface of CO{sub 2} dimer

Energy Technology Data Exchange (ETDEWEB)

Kalugina, Yulia N., E-mail: kalugina@phys.tsu.ru [Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation); Buryak, Ilya A. [Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, Moscow (Russian Federation); Chemistry Department, Lomonosov Moscow State University, Moscow (Russian Federation); Ajili, Yosra [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 Bd Descartes, 77454 Marne-La-Vallée (France); Laboratoire de Spectroscopie Atomique, Moléculaire et Applications - LSAMA Université de Tunis El Manar (Tunisia); Vigasin, Andrei A. [Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, Moscow (Russian Federation); Jaidane, Nejm Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications - LSAMA Université de Tunis El Manar (Tunisia); Hochlaf, Majdi [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 Bd Descartes, 77454 Marne-La-Vallée (France)

2014-06-21

We present an extensive study of the four-dimensional potential energy surface (4D-PES) of the carbon dioxide dimer, (CO{sub 2}){sub 2}. This PES is developed over the set of intermolecular coordinates. The electronic computations are carried out at the explicitly correlated coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)-F12] level of theory in connection with the augmented correlation-consistent aug-cc-pVTZ basis set. An analytic representation of the 4D-PES is derived. Our extensive calculations confirm that “Slipped Parallel” is the most stable form and that the T-shaped structure corresponds to a transition state. Later on, this PES is employed for the calculations of the vibrational energy levels of the dimer. Moreover, the temperature dependence of the dimer second virial coefficient and of the first spectral moment of rototranslational collision-induced absorption spectrum is derived. For both quantities, a good agreement is found between our values and the experimental data for a wide range of temperatures. This attests to the high quality of our PES. Generally, our PES and results can be used for modeling CO{sub 2} supercritical fluidity and examination of its role in planetary atmospheres. It can be also incorporated into dynamical computations of CO{sub 2} capture and sequestration. This allows deep understanding, at the microscopic level, of these processes.

Spontaneous dissociation of Co2(CO8 and autocatalytic growth of Co on SiO2: A combined experimental and theoretical investigation

Directory of Open Access Journals (Sweden)

Kaliappan Muthukumar

2012-07-01

Full Text Available We present experimental results and theoretical simulations of the adsorption behavior of the metal–organic precursor Co2(CO8 on SiO2 surfaces after application of two different pretreatment steps, namely by air plasma cleaning or a focused electron beam pre-irradiation. We observe a spontaneous dissociation of the precursor molecules as well as autodeposition of cobalt on the pretreated SiO2 surfaces. We also find that the differences in metal content and relative stability of these deposits depend on the pretreatment conditions of the substrate. Transport measurements of these deposits are also presented. We are led to assume that the degree of passivation of the SiO2 surface by hydroxyl groups is an important controlling factor in the dissociation process. Our calculations of various slab settings, using dispersion-corrected density functional theory, support this assumption. We observe physisorption of the precursor molecule on a fully hydroxylated SiO2 surface (untreated surface and chemisorption on a partially hydroxylated SiO2 surface (pretreated surface with a spontaneous dissociation of the precursor molecule. In view of these calculations, we discuss the origin of this dissociation and the subsequent autocatalysis.

[Research on the spectral feature and identification of the surface vegetation stressed by stored CO2 underground leakage].

Science.gov (United States)

Chen, Yun-Hao; Jiang, Jin-Bao; Steven, Michael D; Gong, A-Du; Li, Yi-Fan

2012-07-01

With the global climate warming, reducing greenhouse gas emissions becomes a focused problem for the world. The carbon capture and storage (CCS) techniques could mitigate CO2 into atmosphere, but there is a risk in case that the CO2 leaks from underground. The objective of this paper is to study the chlorophyll contents (SPAD value), relative water contents (RWC) and leaf spectra changing features of beetroot under CO2 leakage stress through field experiment. The result shows that the chlorophyll contents and RWC of beetroot under CO2 leakage stress become lower than the control beetroot', and the leaf reflectance increases in the 550 nm region and decreases in the 680nm region. A new vegetation index (R550/R680) was designed for identifying beetroot under CO2 leakage stress, and the result indicates that the vegetation index R550/R680 could identify the beetroots after CO2 leakage for 7 days. The index has strong sensitivity, stability and identification for monitoring the beetroots under CO2 stress. The result of this paper has very important meaning and application values for selecting spots of CCS project, monitoring and evaluating land-surface ecology under CO2 stress and monitoring the leakage spots by using remote sensing.

Colour and chemical changes of the lime wood surface due to CO{sub 2} laser thermal modification

Energy Technology Data Exchange (ETDEWEB)

Kubovský, Ivan, E-mail: kubovsky@tuzvo.sk; Kačík, František

2014-12-01

Highlights: • Influences of CO{sub 2} laser on lime wood surface were studied. • With growth of the irradiation dose brightness decrease and increase of the total colour difference were observed. • Cellulose degradation and loss of hemicelluloses were observed. • Higher values at the input energy lead to accelerating the mutual reaction of the functional groups resulting in the subsequent condensation of lignin. • CO{sub 2} laser irradiation can be used as a new colouring method. - Abstract: We studied colour and main wood components changes of lime wood caused by CO{sub 2} laser beam irradiation. The dry surface of lime wood (Tilia vulgaris L.) was irradiated with the CO{sub 2} laser beam (wavelength of 10.6 μm) at different exposures (expressed as the irradiation dose). Colour changes were monitored by the spectrophotometer, chemical changes were observed by the ATR-FTIR spectroscopy and carbohydrates were analysed by the HPLC method. With the growth of the irradiation dose (from 8.1 to 28.7 J cm{sup −2}) lightness (ΔL{sup *}) decrease and increase of the total colour difference (ΔE{sup *}) were observed. Higher values of the input energy lead to accelerating the mutual reaction of the functional groups resulting in the subsequent condensation of lignin. The total decrease in saccharides at the highest irradiation dose reaches 27.39% of the initial amount of saccharides in the reference sample. We have observed degradation and loss of hemicelluloses.

The relative influence of H2O and CO2 on the primitive surface conditions of Venus

Science.gov (United States)

Salvador, A.; Massol, H.; Davaille, A.; Marcq, E.; Sarda, P.; Chassefiere, E.

2017-12-01

How the volatile content influences the primordial surface conditions of terrestrial planets and, thus, their future geodynamic evolution is an important question to answer. We simulate the secular convective cooling of a 1-D magma ocean (MO) in interaction with its outgassed atmosphere. A first rapid cooling stage, where efficient MO cooling and degassing take place, producing the atmosphere, is followed by a second quasi steady state where the heat flux balance is dominated by the solar flux. The end ofthe rapid cooling stage (ERCS) is reached when the mantle heat flux becomes negligible compared tothe absorbed solar flux. Varying the initial CO2 and H2O contents and the solar distance, we showed that the resulting surface conditions at ERCS strongly depend on these parameters and that water ocean's formation obeys simple scaling laws.Although today's Venus is located beyond the inner edge of the habitable zone due to its high albedo, its high CO2/H2O ratio prevents any water ocean formation.We already showed that depending on the formation time of its cloudcover and resulting albedo, only 0.3 Earth ocean mass might be sufficient to form a water ocean onearly Venus. Here we investigate more precisely these results by taking into account the effect of shortwave radiation on the radiative budget by computing the feedbacks between atmospheric composition and incident stellar flux instead of using a prescribed albedo value.

Why must a solar forcing be larger than a CO2 forcing to cause the same global mean surface temperature change?

International Nuclear Information System (INIS)

Modak, Angshuman; Bala, Govindasamy; Cao, Long; Caldeira, Ken

2016-01-01

Many previous studies have shown that a solar forcing must be greater than a CO 2 forcing to cause the same global mean surface temperature change but a process-based mechanistic explanation is lacking in the literature. In this study, we investigate the physical mechanisms responsible for the lower efficacy of solar forcing compared to an equivalent CO 2 forcing. Radiative forcing is estimated using the Gregory method that regresses top-of-atmosphere (TOA) radiative flux against the change in global mean surface temperature. For a 2.25% increase in solar irradiance that produces the same long term global mean warming as a doubling of CO 2 concentration, we estimate that the efficacy of solar forcing is ∼80% relative to CO 2 forcing in the NCAR CAM5 climate model. We find that the fast tropospheric cloud adjustments especially over land and stratospheric warming in the first four months cause the slope of the regression between the TOA net radiative fluxes and surface temperature to be steeper in the solar forcing case. This steeper slope indicates a stronger net negative feedback and hence correspondingly a larger solar forcing than CO 2 forcing for the same equilibrium surface warming. Evidence is provided that rapid land surface warming in the first four months sets up a land-sea contrast that markedly affects radiative forcing and the climate feedback parameter over this period. We also confirm the robustness of our results using simulations from the Hadley Centre climate model. Our study has important implications for estimating the magnitude of climate change caused by volcanic eruptions, solar geoengineering and past climate changes caused by change in solar irradiance such as Maunder minimum. (letter)

Effects of surface motion and electron-hole pair excitations in CO2 dissociation and scattering on Ni(100)

Science.gov (United States)

Luo, Xuan; Zhou, Xueyao; Jiang, Bin

2018-05-01

The energy transfer between different channels is an important aspect in chemical reactions at surfaces. We investigate here in detail the energy transfer dynamics in a prototypical system, i.e., reactive and nonreactive scattering of CO2 on Ni(100), which is related to heterogeneous catalytic processes with Ni-based catalysts for CO2 reduction. On the basis of our earlier nine-dimensional potential energy surface for CO2/Ni(100), dynamical calculations have been done using the generalized Langevin oscillator (GLO) model combined with local density friction approximation (LDFA), in which the former accounts for the surface motion and the latter accounts for the low-energy electron-hole pair (EHP) excitation. In spite of its simplicity, it is found that the GLO model yields quite satisfactory results, including the significant energy loss and product energy disposal, trapping, and steering dynamics, all of which agree well with the ab initio molecular dynamics ones where many surface atoms are explicitly involved with high computational cost. However, the GLO model fails to describe the reactivity enhancement due to the lattice motion because it intrinsically does not incorporate the variance of barrier height on the surface atom displacement. On the other hand, in LDFA, the energy transferred to EHPs is found to play a minor role and barely alter the dynamics, except for slightly reducing the dissociation probabilities. In addition, vibrational state-selected dissociative sticking probabilities are calculated and previously observed strong mode specificity is confirmed. Our work suggests that further improvement of the GLO model is needed to consider the lattice-induced barrier lowering.

Oxygen adsorption on the Al9Co2(001) surface: first-principles and STM study

International Nuclear Information System (INIS)

Villaseca, S Alarcón; Loli, L N Serkovic; Ledieu, J; Fournée, V; Dubois, J-M; Gaudry, É; Gille, P

2013-01-01

Atomic oxygen adsorption on a pure aluminum terminated Al 9 Co 2 (001) surface is studied by first-principle calculations coupled with STM measurements. Relative adsorption energies of oxygen atoms have been calculated on different surface sites along with the associated STM images. The local electronic structure of the most favourable adsorption site is described. The preferential adsorption site is identified as a ‘bridge’ type site between the cluster entities exposed at the (001) surface termination. The Al–O bonding between the adsorbate and the substrate presents a covalent character, with s–p hybridization occurring between the states of the adsorbed oxygen atom and the aluminum atoms of the surface. The simulated STM image of the preferential adsorption site is in agreement with experimental observations. This work shows that oxygen adsorption generates important atomic relaxations of the topmost surface layer and that sub-surface cobalt atoms strongly influence the values of the adsorption energies. The calculated Al–O distances are in agreement with those reported in Al 2 O and Al 2 O 3 oxides and for oxygen adsorption on Al(111). (paper)

Comparison of regional and ecosystem CO2 fluxes

DEFF Research Database (Denmark)

Gryning, Sven-Erik; Søgaard, Henrik; Batchvarova, Ekaterina

2009-01-01

A budget method to derive the regional surface flux of CO2 from the evolution of the boundary layer is presented and applied. The necessary input for the method can be deduced from a combination of vertical profile measurements of CO2 concentrations by i.e. an airplane, successive radio-soundings......A budget method to derive the regional surface flux of CO2 from the evolution of the boundary layer is presented and applied. The necessary input for the method can be deduced from a combination of vertical profile measurements of CO2 concentrations by i.e. an airplane, successive radio...

CO2 activation through silylimido and silylamido zirconium hydrides supported on N-donor chelating SBA15 surface ligand

KAUST Repository

Pasha, Fahran Ahmad

2016-01-04

Density functional theory calculations and 2D 1H-13C HETCOR solid state NMR spectroscopy prove that CO2 can probe, by its own reactivity, different types of N-donor surface ligands on SBA15-supported ZrIV hydrides: [(≡Si-O-)(≡Si-N=)[Zr]H] and [(≡Si-NH-)(≡Si-X-)[Zr]H2] (X = O or NH). Moreover, [(≡Si-O-)(≡Si-N=)[Zr]H] activates CO2 more efficiently than the other complexes and leads to a carbimato Zr formate.

Decontamination of solid matrices using supercritical CO2: study of contaminant-additives-CO2

International Nuclear Information System (INIS)

Galy, J.

2006-11-01

This work deals with the decontamination of solid matrices by supercritical CO 2 and more particularly with the study of the interactions between the surfactants and the CO 2 in one part, and with the interactions between the contaminant and the surfactants in another part. The first part of this study has revealed the different interactions between the Pluronics molecules and the supercritical CO 2 . The diagrams graphs have shown that the pluronics (PE 6100, PE 8100 and PE 10100) present a solubility in the supercritical CO 2 low but sufficient (0.1% m/m at 25 MPa and 313 K) for the studied application: the treatment of weak quantities of cerium oxide (or plutonium). An empirical approach based on the evolutions of the slops value and of the origin ordinates of the PT diagrams has been carried out to simulate the phase diagrams PT of the Pluronics. A modeling based on the state equations 'SAFT' (Statistical Associating Fluid Theory) has been studied in order to confirm the experimental results of the disorder points and to understand the role of the different blocks 'PEO' and 'PPO' in the behaviour of Pluronics; this modeling confirms the evolution of the slopes value with the 'CO 2 -phily' of the system. The measure of the surface tension in terms of the Pluronics concentration (PE 6100, 81000 and 10100) has shown different behaviours. For the PE 6100, the surface tension decreases when the surfactant concentration increases (at constant pressure and temperature); on the other hand, for the PE 8100 a slop rupture appears and corresponds to the saturation of the interface water/CO 2 and allows then to determine the Interface Saturation Concentration (ISC). The ISC value (at constant pressure and temperature) increases with an increase of the 'CO 2 -phily'). The model hydrophilous medium being an approximation, it has been replaced by a solid polar phase of CeO 2 . A parallel has been established between the evolution of the surface tension between the water and

Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces

DEFF Research Database (Denmark)

Jovanov, Zarko; Hansen, Heine A.; Varela Gasque, Ana Sofia

2016-01-01

Electrolysis could enable the large-scale conversion of CO2 to fuels and small molecules. This perspective discusses the state-of-the-art understanding of CO2 and CO reduction electrocatalysis and provides an overview of the most promising approaches undertaken thus far. We set to explore "bifunc...

Modelling land surface fluxes of CO2 in response to climate change and nitrogen deposition

DEFF Research Database (Denmark)

Hansen, Kristina; Ambelas Skjøth, Carsten; Geels, Camilla

Climate change, land use variations, and impacts of atmospheric nitrogen (N) deposition represent uncertainties for the prediction of future greenhouse gas exchange between land surfaces and the atmosphere as the mechanisms describing nutritional effects are not well developed in climate...... climate feedback mechanisms of CO2 between changes in management, land use practise, and climate change....

Electronic structure, Fermi surface topology and spectroscopic optical properties of LaBaCo{sub 2}O{sub 5.5} compound

Energy Technology Data Exchange (ETDEWEB)

Reshak, A.H. [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, Pilsen 306 14 (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Al-Douri, Y. [Institute of Nano Electronic Engineering, University Malaysia Perlis, 01000 Kangar, Perlis (Malaysia); Khenata, R. [Laboratoire de Physique Quantique et de Modélisation Mathématique (LPQ3M), Département de Technologie, Université de Mascara, Mascara 29000 (Algeria); Khan, Wilayat; Khan, Saleem Ayaz [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, Pilsen 306 14 (Czech Republic); Azam, Sikander, E-mail: sikander.physicst@gmail.com [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, Pilsen 306 14 (Czech Republic)

2014-08-01

We have investigated the electronic band structure, Fermi surface topology, chemical bonding and optical properties of LaBaCo{sub 2}O{sub 5.5} compound. The first-principle calculations based on density functional theory (DFT) by means of the full-potential linearized augmented plane-wave method were employed. The atomic positions of LaBaCo{sub 2}O{sub 5.5} compound were optimized by minimizing the forces acting on atoms. We employed the local density approximation (LDA), generalized gradient approximation (GGA) and Engel–Vosko GGA (EVGGA) to treat the exchange correlation potential by solving Kohn–Sham equations. Electronic structure and bonding properties are studied throughout the calculation of densities of states, Fermi surfaces and charge densities. Furthermore, the optical properties are investigated via the calculation of the dielectric tensor component in order to characterize the linear optical properties. Optical spectra are analyzed by means of the electronic structure, which provides theoretical understanding of the conduction mechanism of the investigated compound. - Highlights: • DFT-FPLAPW method used for calculating the properties of LaBaCo{sub 2}O{sub 5.5} compound. • This study shows that nature of the compound is metallic. • Crystallographic plane which shows covalent character of O–Co bond. • The optical properties were also calculated and analyzed. • The Fermi surface of LaBaCo{sub 2}O{sub 5.5} is composed of five bands crossing along Γ–Z direction.

CO2 Accounting and Risk Analysis for CO2 Sequestration at Enhanced Oil Recovery Sites.

Science.gov (United States)

Dai, Zhenxue; Viswanathan, Hari; Middleton, Richard; Pan, Feng; Ampomah, William; Yang, Changbing; Jia, Wei; Xiao, Ting; Lee, Si-Yong; McPherson, Brian; Balch, Robert; Grigg, Reid; White, Mark

2016-07-19

Using CO2 in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce sequestration costs in the absence of emissions policies that include incentives for carbon capture and storage. This study develops a multiscale statistical framework to perform CO2 accounting and risk analysis in an EOR environment at the Farnsworth Unit (FWU), Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil/gas-water flow and transport in the Morrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2/water injection/production rates, cumulative net CO2 storage, cumulative oil/gas productions, and CO2 breakthrough time. The median and confidence intervals are estimated for quantifying uncertainty ranges of the risk metrics. A response-surface-based economic model has been derived to calculate the CO2-EOR profitability for the FWU site with a current oil price, which suggests that approximately 31% of the 1000 realizations can be profitable. If government carbon-tax credits are available, or the oil price goes up or CO2 capture and operating expenses reduce, more realizations would be profitable. The results from this study provide valuable insights for understanding CO2 storage potential and the corresponding environmental and economic risks of commercial-scale CO2-sequestration in depleted reservoirs.

Carbonation and CO2 uptake of concrete

International Nuclear Information System (INIS)

Yang, Keun-Hyeok; Seo, Eun-A; Tae, Sung-Ho

2014-01-01

This study developed a reliable procedure to assess the carbon dioxide (CO 2 ) uptake of concrete by carbonation during the service life of a structure and by the recycling of concrete after demolition. To generalize the amount of absorbable CO 2 per unit volume of concrete, the molar concentration of carbonatable constituents in hardened cement paste was simplified as a function of the unit content of cement, and the degree of hydration of the cement paste was formulated as a function of the water-to-cement ratio. The contribution of the relative humidity, type of finishing material for the concrete surface, and the substitution level of supplementary cementitious materials to the CO 2 diffusion coefficient in concrete was reflected using various correction factors. The following parameters varying with the recycling scenario were also considered: the carbonatable surface area of concrete crusher-runs and underground phenomena of the decreased CO 2 diffusion coefficient and increased CO 2 concentration. Based on the developed procedure, a case study was conducted for an apartment building with a principal wall system and an office building with a Rahmen system, with the aim of examining the CO 2 uptake of each structural element under different exposure environments during the service life and recycling of the building. As input data necessary for the case study, data collected from actual surveys conducted in 2012 in South Korea were used, which included data on the surrounding environments, lifecycle inventory database, life expectancy of structures, and recycling activity scenario. Ultimately, the CO 2 uptake of concrete during a 100-year lifecycle (life expectancy of 40 years and recycling span of 60 years) was estimated to be 15.5%–17% of the CO 2 emissions from concrete production, which roughly corresponds to 18%–21% of the CO 2 emissions from the production of ordinary Portland cement. - Highlights: • CO 2 uptake assessment approach owing to the

Improved solar-driven photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} prepared in-situ

Energy Technology Data Exchange (ETDEWEB)

Zhong, Junbo, E-mail: junbozhong@163.com [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Li, Jianzhang, E-mail: lschmanuscript@163.com [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Huang, Shengtian; Cheng, Chaozhu; Yuan, Wei [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Li, Minjiao [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Sichuan Provincial Academician (Expert) Workstation, Sichuan University of Science and Engineering, Zigong 643000 (China); Ding, Jie [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China)

2016-05-15

Highlights: • Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} photocatalysts were prepared in-situ. • The photo-induced charge separation rate has been greatly increased. • The photocatalytic activity has been greatly promoted. - Abstract: Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} composites have been fabricated in-situ via a facile parallel flaw co-precipitation method. The specific surface area, structure, morphology, and the separation rate of photo-induced charge pairs of the photocatalysts were characterized by Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy(DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and surface photovoltage (SPV) spectroscopy, respectively. XRD patterns and DRS demonstrated that Ag{sub 2}CO{sub 3} has no effect on the crystal phase and bandgap of (BiO){sub 2}CO{sub 3}. The existence of Ag{sub 2}CO{sub 3} in the composites enhances the separation rate of photo-induced charge pairs of the photocatalysts. The photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} was evaluated by the decolorization of methyl orange (MO) aqueous solution under simulated solar irradiation. It was found that the simulated solar-induced photocatalytic activity of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} copmposites was significantly improved, which was mainly attributed to the enhanced surface area and the separation rate of photo-induced charge pairs.

Controlling mechanisms of surface partial pressure of CO2 in Jiaozhou Bay during summer and the influence of heavy rain

Science.gov (United States)

Li, Yunxiao; Yang, Xufeng; Han, Ping; Xue, Liang; Zhang, Longjun

2017-09-01

Due to the combined effects of natural processes and human activities, carbon source/sink processes and mechanisms in the coastal ocean are becoming more and more important in current ocean carbon cycle research. Based on differences in the ratio of total alkalinity (TA) to dissolved inorganic carbon (DIC) associated with terrestrial input, biological process (production and respiration), calcium carbonate (CaCO3) process (precipitation and dissolution) and CO2 evasion/invasion, we discuss the mechanisms controlling the surface partial pressure of CO2 (pCO2) in Jiaozhou Bay (JZB) during summer and the influence of heavy rain, via three cruises performed in mid-June, early July and late July of 2014. In mid-June and in early July, without heavy rain or obvious river input, sea surface pCO2 ranged from 521 to 1080 μatm and from 547 to 998 μatm, respectively. The direct input of DIC from sewage and the intense respiration produced large DIC additions and the highest pCO2 values in the northeast of the bay near the downtown of Qingdao. However, in the west of the bay, significant CaCO3 precipitation led to DIC removal but no obvious increase in pCO2, which was just close to that in the central area. Due to the shallow depth and longer water residence time in this region, this pattern may be related to the sustained release of CO2 into the atmosphere. In late July, heavy rain promoted river input in the western and eastern portions of JZB. Strong primary production led to a significant decrease in pCO2 in the western area, with the lowest pCO2 value of 252 μatm. However, in the northeastern area, the intense respiration remained, and the highest pCO2 value was 1149 μatm. The average air-sea CO2 flux in mid-June and early July was 20.23 mmol m- 2 d- 1 and 23.56 mmol m- 2 d- 1, respectively. In contrast, in late July, sources became sinks for atmospheric CO2 in the western and central areas of the bay, halving the average air-sea CO2 flux to a value of 10.58 mmol m- 2

SFG investigation of adsorbed CO and NO on NiO(111) surface

Energy Technology Data Exchange (ETDEWEB)

Bandara, Athula; Dobashi, Shinsaku; Kubota, Jun; Onda, Ken; Wada, Akihide; Domen, Kazunari; Hirose, Chiaki [Tokyo Inst. of Tech., Yokohama (Japan). Research Lab. of Resources Utilization; Kano, S.S.

1997-07-01

Adsorption structures of CO and NO on the NiO(111) film grown on Ni(111) crystal have been investigated by sum frequency generation (SFG) spectroscopy and infrared reflection absorption spectroscopy (IRAS). The CO stretching band of adsorbed CO on NiO(111) was observed at 2144 cm{sup -1} on the SFG spectra for both p- and s-polarized visible light. However, adsorbed NO on NiO(111) was observed at 1805 cm{sup -1} on the SFG spectra only for the p-polarized visible light. The results suggest that the adsorbed CO molecule was tilted from the surface normal but the NO molecule was perpendicular to the surface. These orientations of CO and NO reflect the surface structure of NiO(111) which has (2 x 2)-reconstructed microfacets. Adsorption of CO on Ni(111) instead of NiO(111) was also examined by SFG and IRAS. Absorption bands due to linear and bridged CO were observed at 2076 and 1918 cm{sup -1}, respectively, by IRAS. On the other hand, the linear CO molecules on Ni(111) gave an SFG peak at 2076 cm{sup -1} only for the p-polarized visible light indicating the CO molecules are perpendicular to the surface, and bridged CO molecules did not give any SFG signal. The absence of the bridged CO signal is believed to be due to the smaller Raman tensor of bridged CO. (author)

SFG investigation of adsorbed CO and NO on NiO(111) surface

International Nuclear Information System (INIS)

Bandara, Athula; Dobashi, Shinsaku; Kubota, Jun; Onda, Ken; Wada, Akihide; Domen, Kazunari; Hirose, Chiaki; Kano, S.S.

1997-01-01

Adsorption structures of CO and NO on the NiO(111) film grown on Ni(111) crystal have been investigated by sum frequency generation (SFG) spectroscopy and infrared reflection absorption spectroscopy (IRAS). The CO stretching band of adsorbed CO on NiO(111) was observed at 2144 cm -1 on the SFG spectra for both p- and s-polarized visible light. However, adsorbed NO on NiO(111) was observed at 1805 cm -1 on the SFG spectra only for the p-polarized visible light. The results suggest that the adsorbed CO molecule was tilted from the surface normal but the NO molecule was perpendicular to the surface. These orientations of CO and NO reflect the surface structure of NiO(111) which has (2 x 2)-reconstructed microfacets. Adsorption of CO on Ni(111) instead of NiO(111) was also examined by SFG and IRAS. Absorption bands due to linear and bridged CO were observed at 2076 and 1918 cm -1 , respectively, by IRAS. On the other hand, the linear CO molecules on Ni(111) gave an SFG peak at 2076 cm -1 only for the p-polarized visible light indicating the CO molecules are perpendicular to the surface, and bridged CO molecules did not give any SFG signal. The absence of the bridged CO signal is believed to be due to the smaller Raman tensor of bridged CO. (author)

Enhancement of electrochemical performance of LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 by surface modification with MnO_2

International Nuclear Information System (INIS)

Guo, Xin; Cong, Li-Na; Zhao, Qin; Tai, Ling-Hua; Wu, Xing-Long; Zhang, Jing-Ping; Wang, Rong-Shun; Xie, Hai-Ming; Sun, Li-Qun

2015-01-01

LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 is successfully coated with MnO_2 by a chemical deposition method. The X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM) results demonstrate that MnO_2 forms a thin layer on the surface of LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 without destroying the crystal structure of the core material. Compared with pristine LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2, the MnO_2-coated sample shows enhanced electrochemical performance especially the rate capability. Even at a current density of 750 mA g"−"1, the discharge capacity of MnO_2-coated LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 is 155.15 mAh g"−"1, while that of the pristine electrode is only 132.84 mAh g"−"1 in the range of 2.5–4.5 V. The cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) curves show that the MnO_2 coating layer reacts with Li"+ during cycling, which is responsible for the higher discharge capacity of MnO_2-coated LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2. Electrochemical impedance spectroscopy (EIS) results confirmed that the MnO_2 coating layer plays an important role in reducing the charge transfer resistance on the electrolyte–electrode interfaces. - Highlights: • MnO_2 coated LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 cathode material is synthesized for the first time. • MnO_2 offers available sites for insertion of extracted lithium. • The preserved surface and crystal structures results in the improved kinetics.

Structure sensitivity of CO dissociation on Rh surfaces

DEFF Research Database (Denmark)

Mavrikakis, Manos; Baumer, M.; Freund, H.J.

2002-01-01

than the flat surface, but the effect is considerably weaker than the effect of surface structure on the dissociation barrier. Our findings are compared with available experimental data, and the consequences for CO activation in methanation and Fischer-Tropsch reactions are discussed.......Using periodic self-consistent density functional calculations it is shown that the barrier for CO dissociation is similar to120 kJ/mol lower on the stepped Rh(211) surface than on the close-packed Rh(111) surface. The stepped surface binds molecular CO and the dissociation products more strongly...

Supercritical CO2 uptake by nonswelling phyllosilicates.

Science.gov (United States)

Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

2018-01-30

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

Structure and properties of optical-discharge plasma in CO2-laser beam near target surface

Science.gov (United States)

Danshchikov, Ye. V.; Dymshakov, V. A.; Lebedev, F. V.; Ryazanov, A. V.

1986-05-01

An experimental study of optical-discharge plasma in a CO2-laser beam at a target surface was made for the purpose of exploring the not yet understood role of this plasma in the laser-target interaction process. Such a plasma was produced by means of a quasi-continuous CO2-laser with an unstable resonator, its power being maintained constant for 1 ms periods. Its radiation was focused on the surfaces of thick and seeding thin Al, Ti, and Ta targets inclined at an approximately 70 deg. angle to the beam, inside a hermetic chamber containing air, argon, or helium under atmospheric pressure. The radiation intensity distribution over the focal plane and the nearest caustic surface in the laser beam was measured along with the plasma parameters, the latter by the methods of spectral analysis and photoelectric recording. The instrumentation for this purpose included an MDR-3 monochromator with an entrance slit, a double electron-optical converter, a memory oscillograph, and an SI-10-30 ribbon lamp as radiation reference standard. The results yielded integral diametral intensity distributions of the emission lines Ti-II (457.2 nm), Ti-I (464 nm), Ar-II (462 nm), radial and axial temperature profiles of optical discharge in metal vapor in surrounding gas, and the radial temperature profile of irradiated metal surface at successive instants of time. The results reveal marked differences between the structures and the properties of optical-discharge plasma in metal vapor and in surrounding gas, optical discharge in the former being characterized by localization within the laser beam and optical discharge in the latter being characterized by a drift away from the target.

Subsurface watering resulted in reduced soil N2O and CO2 emissions and their global warming potentials than surface watering

Science.gov (United States)

Wei, Qi; Xu, Junzeng; Yang, Shihong; Liao, Linxian; Jin, Guangqiu; Li, Yawei; Hameed, Fazli

2018-01-01

Water management is an important practice with significant effect on greenhouse gases (GHG) emission from soils. Nitrous oxide (N2O) and carbon dioxide (CO2) emissions and their global warming potentials (GWPs) from subsurface watering soil (SUW) were investigated, with surface watering (SW) as a control. Results indicated that the N2O and CO2 emissions from SUW soils were somewhat different to those from SW soil, with the peak N2O and CO2 fluxes from SUW soil reduced by 28.9% and 19.4%, and appeared 72 h and 168 h later compared with SW. The fluxes of N2O and CO2 from SUW soils were lower than those from SW soil in both pulse and post-pulse periods, and the reduction was significantly (p0.1) lower that from SW soil. Moreover, N2O and CO2 fluxes from both watering treatments increased exponentially with increase of soil water-filled pore space (WFPS) and temperature. Our results suggest that watering soil from subsurface could significantly reduce the integrative greenhouse effect caused by N2O and CO2 and is a promising strategy for soil greenhouse gases (GHGs) mitigation. And the pulse period, contributed most to the reduction in emissions of N2O and CO2 from soils between SW and SUW, should be a key period for mitigating GHGs emissions. Response of N2O and CO2 emissions to soil WFPS and temperature illustrated that moisture was the dominant parameters that triggering GHG pulse emissions (especially for N2O), and temperature had a greater effect on the soil microorganism activity than moisture in drier soil. Avoiding moisture and temperature are appropriate for GHG emission at the same time is essential for GHGs mitigation, because peak N2O and CO2 emission were observed only when moisture and temperature are both appropriate.

Enhanced electrocatalysis performance of amorphous electrolytic carbon from CO2 for oxygen reduction by surface modification in molten salt

International Nuclear Information System (INIS)

Chen, Zhigang; Gu, Yuxing; Du, Kaifa; Wang, Xu; Xiao, Wei; Mao, Xuhui; Wang, Dihua

2017-01-01

Highlights: •The potential of electrolytic carbon as catalyst for oxygen reduction was evaluated. •A molten salt method for electrolytic-carbon modification was demonstrated. •The electrolytic carbon was activated for the ORR by the molten salt sulfidation. •Sulfur and cobalt dual modification further improved the ORR activity of the carbon. -- Abstract: The electrolytic carbon (E-carbon) derived from greenhouse gas CO 2 in molten carbonates at mild temperature possesses high electrical conductivity and suitable specific surface area. In this work, its potential as catalyst is investigated towards oxygen reduction reaction (ORR). It is revealed that the pristine E-carbon has no electrocatalytic activity for the ORR due to its high surface content of carboxyl group. The carbon was then treated in a Li 2 SO 4 containing Li 2 CO 3 -Na 2 CO 3 -K 2 CO 3 molten salt at 550 °C. Sulfur modified E-carbon was obtained in the melt via a galvanic sulfidation reaction, in which Li 2 SO 4 served as a nontoxic sulfur source and an oxidant. The sulfur modified E-carbon showed a significantly improved electrocatalytic activity. Subsequently, a sulfur/cobalt dual modified carbon with much higher catalysis activity was successfully prepared by treating an E-carbon/CoSO 4 composite in the same melt. The dual modified E-carbon showed excellent catalytic performance with activity close to the commercial Pt/C catalyst but a high tolerance towards methanol.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

Science.gov (United States)

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-01-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

Surface-reconstructed Cu Electrode via a Facile Electrochemical Anodization-Reduction Process for Low Overpotential CO 2 reduction

KAUST Repository

Min, Shixiong; Yang, Xiulin; Lu, Ang-Yu; Tseng, Chien-Chih; Hedhili, Mohamed N.; Lai, Zhiping; Li, Lain-Jong; Huang, Kuo-Wei

2017-01-01

A high-surface-area Cu electrode, fabricated by a simple electrochemical anodization-reduction method, exhibits high activity and selectivity for CO2 reduction at low overpotential in 0.1 M KHCO3 solution. A faradaic efficiency of 37% for HCOOH

Interaction of cw CO2 laser radiation with plasma near-metallic substrate surface

Science.gov (United States)

Azharonok, V. V.; Astapchik, S. A.; Zabelin, Alexandre M.; Golubev, Vladimir S.; Golubev, V. S.; Grezev, A. N.; Filatov, Igor V.; Chubrik, N. I.; Shimanovich, V. D.

2000-07-01

Optical and spectroscopic methods were used in studying near-surface plasma that is formed under the effect CW CO2 laser of (2- 5)x106W/cm2 power density upon stainless steel in He and Ar shielding gases. The variation of plume spatial structure with time has been studied, the outflow of gas-vapor jets from the interaction area has been characterized. The spectra of plasma plume pulsations have been obtained for the frequency range Δf = 0-1 MHz. The temperature and electron concentration of plasma plume have been found under radiation effect upon the target of stainless steel. Consideration has been given to the most probable mechanisms of CW laser radiation-metal non-stationary interaction.

A shallow subsurface controlled release facility in Bozeman, Montana, USA, for testing near surface CO₂ detection techniques and transport models

Energy Technology Data Exchange (ETDEWEB)

Spangler, Lee H. [Montana State Univ., Bozeman, MT (United States). Dept. of Chemistry and Biochemistry; Dobeck, Laura M. [Montana State Univ., Bozeman, MT (United States). Dept. of Chemistry and Biochemistry; Repasky, Kevin S. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Nehrir, Amin R. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Humphries, Seth D. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Barr, Jamie L. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Keith, Charlie J. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Shaw, Joseph A. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Rouse, Joshua H. [Montana State Univ., Bozeman, MT (United States). Dept. of Electrical and Computer Engineering; Cunningham, Alfred B. [Montana State Univ., Bozeman, MT (United States). Dept. of Civil Engineering; Benson, Sally M. [Stanford Univ., CA (United States). Global Climate and Energy Project; Oldenburg, Curtis M. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Div.; Lewicki, Jennifer L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Div.; Wells, Arthur W. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Div.; Diehl, J. Rodney [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Div.; Strazisar, Brian R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Div.; Fessenden, Julianna E. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Div. of Earth and Environmental Sciences; Rahn, Thom A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Div. of Earth and Environmental Sciences; Amonette, James E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Barr, Jon L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pickles, William L. [Univ. of California, Santa Cruz, CA (United States). Earth and Planetary Sciences; Jacobson, James D. [Univ. of California, Santa Cruz, CA (United States). Earth and Planetary Sciences; Silver, Eli A. [Univ. of California, Santa Cruz, CA (United States). Earth and Planetary Sciences; Male, Erin J. [Univ. of California, Santa Cruz, CA (United States). Earth and Planetary Sciences; Rauch, Henry W. [Univ. of West Virginia, Morgantown, WV (United States). Dept. of Geology and Geography; Gullickson, Kadie S. [Montana State Univ., Bozeman, MT (United States). Dept. of Chemistry and Biochemistry; Trautz, Robert [Electric Power Research Inst. (EPRI), Palo Alto, CA (United States); Kharaka, Yousif [U.S. Geological Survey, Menlo Park, CA (United States); Birkholzer, Jens [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Div.; Wielopolski, Lucien [Brookhaven National Lab. (BNL), Upton, NY (United States)

2010-03-01

A controlled field pilot has been developed in Bozeman, Montana, USA, to study near surface CO₂ transport and detection technologies. A slotted horizontal well divided into six zones was installed in the shallow subsurface. The scale and CO₂ release rates were chosen to be relevant to developing monitoring strategies for geological carbon storage. The field site was characterized before injection, and CO₂ transport and concentrations in saturated soil and the vadose zone were modeled. Controlled releases of CO₂ from the horizontal well were performed in the summers of 2007 and 2008, and collaborators from six national labs, three universities, and the U. S. Geological Survey investigated movement of CO₂ through the soil, water, plants, and air with a wide range of near surface detection techniques. An overview of these results will be presented.

A sensitivity analysis on seismic tomography data with respect to CO2 saturation of a CO2 geological sequestration field

Science.gov (United States)

Park, Chanho; Nguyen, Phung K. T.; Nam, Myung Jin; Kim, Jongwook

2013-04-01

Monitoring CO2 migration and storage in geological formations is important not only for the stability of geological sequestration of CO2 but also for efficient management of CO2 injection. Especially, geophysical methods can make in situ observation of CO2 to assess the potential leakage of CO2 and to improve reservoir description as well to monitor development of geologic discontinuity (i.e., fault, crack, joint, etc.). Geophysical monitoring can be based on wireline logging or surface surveys for well-scale monitoring (high resolution and nallow area of investigation) or basin-scale monitoring (low resolution and wide area of investigation). In the meantime, crosswell tomography can make reservoir-scale monitoring to bridge the resolution gap between well logs and surface measurements. This study focuses on reservoir-scale monitoring based on crosswell seismic tomography aiming describe details of reservoir structure and monitoring migration of reservoir fluid (water and CO2). For the monitoring, we first make a sensitivity analysis on crosswell seismic tomography data with respect to CO2 saturation. For the sensitivity analysis, Rock Physics Models (RPMs) are constructed by calculating the values of density and P and S-wave velocities of a virtual CO2 injection reservoir. Since the seismic velocity of the reservoir accordingly changes as CO2 saturation changes when the CO2 saturation is less than about 20%, while when the CO2 saturation is larger than 20%, the seismic velocity is insensitive to the change, sensitivity analysis is mainly made when CO2 saturation is less than 20%. For precise simulation of seismic tomography responses for constructed RPMs, we developed a time-domain 2D elastic modeling based on finite difference method with a staggered grid employing a boundary condition of a convolutional perfectly matched layer. We further make comparison between sensitivities of seismic tomography and surface measurements for RPMs to analysis resolution

CO2 regeneration performance enhancement by nanoabsorbents for energy conversion application

International Nuclear Information System (INIS)

Lee, Jung Hun; Lee, Jae Won; Kang, Yong Tae

2016-01-01

Graphical abstract: (a) Optical profiling image of the surface of copper after regeneration process in nanoabsorbents, Al 2 O 3 (45 nm, 0.01 vol%). (b) The number of regeneration sites by the nanoabsorbents. - Highlights: • CO 2 regeneration performance is enhanced by using Al 2 O 3 nanoabsorbents. • CO 2 regeneration process on the heating surface is visualized in nanoabsorbents. • Surface modification by nanoabsorbents has a greater effect than the nanoparticle size. • The mechanism of surface effect is the most plausible to explain the regeneration performance enhancement. - Abstract: Due to the recent increase in the consumption of energy and the use of fossil fuels, global warming has become a serious issue. To address this problem, CO 2 gas, which is the major element of the greenhouse gases, should be captured, regenerated and converted to useful fuels. The Integrated Gasification Combined Cycle (IGCC) and cement process generate large amount of CO 2 , which are controlled through pre-combustion capture. However, this method has a disadvantage because the system temperature should be decreased to −20 °C or lower. Therefore, the development of new absorbent is required to reduce the energy consumed for refrigeration. There is a study that improved the CO 2 absorption performance by adding Al 2 O 3 nanoparticles to methanol. However, studies on the regeneration of CO 2 in nanofluid absorbents (nanoabsorbents) are insufficient. Therefore, in this study, the CO 2 regeneration performance in Al 2 O 3 nanoabsorbents is evaluated. It is found that the regeneration performance of CO 2 is improved by 16% by using nanoabsorbents compared to methanol. Furthermore, the CO 2 regeneration characteristics of nanoabsorbents are analyzed by considering the detachment time of CO 2 bubbles from the surface, the cross-sectional area of CO 2 bubble, and the number of regeneration sites through the CO 2 regeneration and bubble visualization experiments. It is concluded

Caractéristiques des substrats et interactions dans les filières de co-digestion : cas particulier des co-substrats d’origine agro-industrielle

Directory of Open Access Journals (Sweden)

GIRAULT, Romain

2013-10-01

Full Text Available Pour assurer l’équilibre économique des unités de méthanisation, l’ajout de co-substrats est en général nécessaire. Pour les choisir, deux questions se posent aux porteurs de projets : quelles sont les caractéristiques des co-substrats disponibles et quel est l’impact des mélanges sur le fonctionnement du digesteur. Le présent article se propose de répondre à ces questions sur la base des résultats du projet Biodecol2.

Modeling Silicate Weathering for Elevated CO2 and Temperature

Science.gov (United States)

Bolton, E. W.

2016-12-01

A reactive transport model (RTM) is used to assess CO2 drawdown by silicate weathering over a wide range of temperature, pCO2, and infiltration rates for basalts and granites. Although RTM's have been used extensively to model weathering of basalts and granites for present-day conditions, we extend such modeling to higher CO2 that could have existed during the Archean and Proterozoic. We also consider a wide range of surface temperatures and infiltration rates. We consider several model basalt and granite compositions. We normally impose CO2 in equilibrium with the various atmospheric ranges modeled and CO2 is delivered to the weathering zone by aqueous transport. We also consider models with fixed CO2 (aq) throughout the weathering zone as could occur in soils with partial water saturation or with plant respiration, which can strongly influence pH and mineral dissolution rates. For the modeling, we use Kinflow: a model developed at Yale that includes mineral dissolution and precipitation under kinetic control, aqueous speciation, surface erosion, dynamic porosity, permeability, and mineral surface areas via sub-grid-scale grain models, and exchange of volatiles at the surface. Most of the modeling is done in 1D, but some comparisons to 2D domains with heterogeneous permeability are made. We find that when CO2 is fixed only at the surface, the pH tends toward higher values for basalts than granites, in large part due to the presence of more divalent than monovalent cations in the primary minerals, tending to decrease rates of mineral dissolution. Weathering rates increase (as expected) with increasing CO2 and temperature. This modeling is done with the support of the Virtual Planetary Laboratory.

AN ARTIFICIAL INTELLIGENCE APPROACH FOR THE PREDICTION OF SURFACE ROUGHNESS IN CO2 LASER CUTTING

Directory of Open Access Journals (Sweden)

MILOŠ MADIĆ

2012-12-01

Full Text Available In laser cutting, the cut quality is of great importance. Multiple non-linear effects of process parameters and their interactions make very difficult to predict cut quality. In this paper, artificial intelligence (AI approach was applied to predict the surface roughness in CO2 laser cutting. To this aim, artificial neural network (ANN model of surface roughness was developed in terms of cutting speed, laser power and assist gas pressure. The experimental results obtained from Taguchi’s L25 orthogonal array were used to develop ANN model. The ANN mathematical model of surface roughness was expressed as explicit nonlinear function of the selected input parameters. Statistical results indicate that the ANN model can predict the surface roughness with good accuracy. It was showed that ANNs may be used as a good alternative in analyzing the effects of cutting parameters on the surface roughness.

Oxidation of steel heated in CO{sub 2} medium under pressure; Oxydation d'un acier ordinaire chauffe dans le gaz carbonique sous pression

Energy Technology Data Exchange (ETDEWEB)

Darras, R; Leclercq, D; Bunard, C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1958-07-01

Behaviour of low-alloyed steels heated in CO{sub 2} medium under pressure is reported. Tests are carried out in the range of erature reached in the CO{sub 2} cooled reactors (vessel, thermal shield, pipes). The observed weight increases are small, even after more than a thousand hours of heating at 350 deg. C, but oxidation curve looks like progressing linearly. Furthermore, the oxide formed under a pressure of 15 kg/cm{sup 2} is undoubtedly more compact and adherent than the one formed under a pressure of 1 kg/cm{sup 2}. Finally, for practical use, CO{sub 2} steel pipes surface has to be sand blast and pickled. A following phosphatizing protects it from atmospheric corrosion during assembling, but these treatments have no influence on the behaviour of these steels heated in CO{sub 2}. (author)Fren. [French] On etudie le comportement d'aciers au carbone faiblement allies, chauffes dans le gaz carbonique sous pression, aux temperatures atteintes dans les reacteurs refroidis par ce gaz (caisson, bouclier thermique, canalisations). Les augmentations de poids observees sont faibles, meme apres plus de 1000 heures de chauffage a 350 deg. C, mais l'oxydation semble se poursuivre lineairement. De plus, l'oxyde forme dans le gaz carbonique sous pression de 15 kg/cm{sup 2} est nettement plus compact et adherent que celui forme sous pression atmospherique de gaz carbonique. Enfin, dans la pratique, les surfaces d'acier du circuit de gaz carbonique sont necessairement sablees ou decapees; une phosphatation ulterieure le protege de la corrosion atmospherique pendant le montage. Ces traitements sont sans influence sur le comportement de ces aciers dans le gaz carbonique a chaud. (auteur)

Variations and trends of CO2 in the surface seawater in the Southern Ocean south of Australia between 1969 and 2002

International Nuclear Information System (INIS)

Yoshikawa-Inoue, Hisayuki; Ishii, M.

2005-01-01

Measurements of the partial pressure of CO 2 in surface seawater (pCO sw 2 ) were made in the Southern Ocean south of Australia during four cruises in January to February 1969, December 1983 to January 1984, December 1994 to January 1995 and January 2002. The spatial distribution of pCO sw 2 for the four cruises showed the same pattern north of the Sub-Antarctic Front (SAF), while year-to-year changes were noted south of the SAF. We evaluated the long-term trend of the pCO sw 2 representative of the zone between oceanographic fronts by taking into account changes in the seasonal variation in pCO sw 2 and the long-term increase of the sea-surface temperature (SST) of the Southern Hemisphere. The observed growth rate of pCO sw 2 was 0.7 ± 0.1 μatm/yr at its minimum, which was observed at the SST of 15 deg C north of the Subtropical Front (STF), 1.0 ± 0.5 μatm/yr in the Sub-Antarctic Zone (SAZ) between STF and SAF, 1.5 ± 0.4 μatm/yr in the Polar Frontal Zone (PFZ) between SAF and the Polar Front (PF) and 1.8 ± 0.2 μμatm/yr in the Polar Zone (PZ) between PF and 62 deg S, determined as the northern edge of the Seasonal Sea Ice Zone (SSIZ) on the basis of surface salinity and satellite images. These increases were caused by the uptake of anthropogenic CO 2 as well as variations in the thermodynamic temperature effect, ocean transport and biological activity. In the SSIZ between 62 and 66.5 deg S, we could not clearly evaluate the long-term trend of pCO sw 2 due to the remarkable CO 2 drawdown due to biological activity in January 2002. The relatively low growth rates of pCO sw 2 close to the STF and in the SAZ are probably associated with the formation of Subtropical Mode Water and Sub-Antarctic Mode Water in their respective zones. Between the north of the STF and the PZ, the growth rate of total dissolved inorganic carbon was calculated to be about 0.5-0.8 μmol/kg/yr via the buffer factor

Retour d'expérience sur la co-construction d'un guide sur la gouvernance territoriale

OpenAIRE

Maurel, P.; Barbe, E.; Rey-Valette, H.; Chia, E.; Soulard, C.; Michel, L.; Pinto, M.

2014-01-01

/ La gouvernance territoriale est devenue un enjeu majeur et une question centrale pour la mise en oeuvre des politiques publiques. Dans le cadre du programme de recherche en partenariat PSDR, un collectif hybride composé de chercheurs, de professionnels du développement territorial et d'acteurs locaux s'est réuni au sein du projet Gouv.Innov. En s'appuyant sur plusieurs terrains d'étude, ce collectif a progressivement construit une définition de la gouvernance territoriale ainsi qu'une grill...

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO_2, CH_4, H_2 adsorptions and high CO_2/N_2 selectivity

International Nuclear Information System (INIS)

Modak, Arindam; Bhaumik, Asim

2015-01-01

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m"2 g"−"1 and micropore volume of 0.85 cm"3 g"−"1 has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO_2 (7.6 mmol g"−"1) and CH_4 (2.4 mmol g"−"1) at 1 atm, 273 K together with very good selectivity for the CO_2/N_2 (30.2) separation. Furthermore, low pressure (1 atm) H_2 (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m"2 g"−"1 has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO_2 (7.6 mmol g"−"1), CH_4 (2.4 mmol g"−"1) and H_2 (2.6 wt%) at 1 atm together with very good selectivity for CO_2. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m"2 g"−"1. • High CO2 uptake (7.6 mmol g"−"1) and CO_2/N_2 selectivity (30.2). • Porous carbon also showed high H_2 (2.6 wt%) and H_2O (57.4 wt%) uptakes.

Magnetoresistance in Co/2D MoS2/Co and Ni/2D MoS2/Ni junctions.

Science.gov (United States)

Zhang, Han; Ye, Meng; Wang, Yangyang; Quhe, Ruge; Pan, Yuanyuan; Guo, Ying; Song, Zhigang; Yang, Jinbo; Guo, Wanlin; Lu, Jing

2016-06-28

Semiconducting single-layer (SL) and few-layer MoS2 have a flat surface, free of dangling bonds. Using density functional theory coupled with non-equilibrium Green's function method, we investigate the spin-polarized transport properties of Co/2D MoS2/Co and Ni/2D MoS2/Ni junctions with MoS2 layer numbers of N = 1, 3, and 5. Well-defined interfaces are formed between MoS2 and metal electrodes. The junctions with a SL MoS2 spacer are almost metallic owing to the strong coupling between MoS2 and the ferromagnets, while those are tunneling with a few layer MoS2 spacer. Both large magnetoresistance and tunneling magnetoresistance are found when fcc or hcp Co is used as an electrode. Therefore, flat single- and few-layer MoS2 can serve as an effective nonmagnetic spacer in a magnetoresistance or tunneling magnetoresistance device with a well-defined interface.

A novel heterogeneous system for sulfate radical generation through sulfite activation on a CoFe{sub 2}O{sub 4} nanocatalyst surface

Energy Technology Data Exchange (ETDEWEB)

Liu, Zizheng [School of Civil Engineering, Wuhan University, Wuhan, 430072 (China); Yang, Shaojie; Yuan, Yanan; Xu, Jing; Zhu, Yifan [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China); Li, Jinjun, E-mail: ljj0410@163.com [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China); Wu, Feng, E-mail: fengwu@whu.edu.cn [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China)

2017-02-15

Highlights: • CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system is proposed as a new system of sulfate radical based AOPs. • Alkaline pH favors the activation of sulfite on CoFe{sub 2}O{sub 4} surface to produce oxysulfur radicals. • Generation of Co−OH complexes on the surface of CoFe{sub 2}O{sub 4} is the main factor for sulfite activation. • Degradation of organic contaminants by CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system were achieved. • Main intermediates and pathways for the degradation of metoprolol were identified. - Abstract: Heterogeneous catalytic activation is important for potential application of new sulfate-radical-based advanced oxidation process using sulfite as source of sulfate radical. We report herein a heterogeneous system for sulfite activation by CoFe{sub 2}O{sub 4} nanocatalyst for metoprolol removal. Factors that influence metoprolol removal were investigated, including pH and initial concentrations of components. The CoFe{sub 2}O{sub 4} nanocatalyst was characterized by X-ray diffractometry (XRD) and transmission electron microscopy (TEM), and the catalytic stability was tested by consecutive runs. Radicals generated in the CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system were identified through radical quenching experiments and by electron spin resonance (ESR). The catalytic mechanism was elucidated further by X-ray photoelectron spectroscopy (XPS). The catalytic process was dependent on initial pH, and more than 80% of the metoprolol can be removed at pH 10.0 following the Langmubir-Hinshelwood equation. The generation of Co-OH complexes on the CoFe{sub 2}O{sub 4} surface was crucial for sulfite activation. SO{sub 4}{sup ·−} was verified to be the main oxidative species responsible for metoprolol degradation. Other organic pollutants, such as sulfanilamide, sulfasalazine, 2-nitroaniline, sulfapyridine, aniline, azo dye X-3B and 4-chloroaniline, could also be removed in this CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system. The

The effect of Pd ensemble structure on the O2 dissociation and CO oxidation mechanisms on Au—Pd(100) surface alloys

Science.gov (United States)

Oǧuz, Ismail-Can; Mineva, Tzonka; Guesmi, Hazar

2018-01-01

The reactivity of various Pd ensembles on the Au—Pd(100) alloy catalyst toward CO oxidation was investigated by using density functional theory (DFT). This study was prompted by the search for efficient catalysts operating at low temperature for the CO oxidation reaction that is of primary environmental importance. To this aim, we considered Pd modified Au(100) surfaces including Pd monomers, Pd dimers, second neighboring Pd atoms, and Pd chains in a comparative study of the minimum energy reaction pathways. The effect of dispersion interactions was included in the calculations of the O2 dissociation reaction pathway by using the DFT-D3 scheme. The addition of the dispersion interaction strongly improves the adsorption ability of O2 on the Au—Pd surface but does not affect the activation energy barriers of the Transitions States (TSs). As for O2 to dissociate, it is imperative that the TS has lower activation energy than the O2 desorption energy. DFT-D3 is found to favor, in some cases, O2 dissociation on configurations being identified from uncorrected DFT calculations as inactive. This is the case of the second neighboring Pd configuration for which uncorrected DFT predicts positive Gibbs free energy (ΔG) of the O2 adsorption, therefore an endergonic reaction. With the addition of D3 correction, ΔG becomes negative that reveals a spontaneous O2 adsorption. Among the investigated Au—Pd (100) ensembles, the Pd chain dissociates most easily O2 and highly stabilizes the dissociated O atoms; however, it has an inferior reactivity toward CO oxidation and CO2 formation. Indeed, CO strongly adsorbs on the palladium bridge sites and therefore poisoning the surface Pd chain. By contrast, the second neighboring Pd configuration that shows somewhat lower ability to dissociate O2 turns out to be more reactive in the CO2 formation step. These results evidence the complex effect of Pd ensembles on the CO oxidation reaction. Associative CO oxidation proceeds with high

Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration.

Science.gov (United States)

Liang, Yunfeng; Tsuji, Shinya; Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi

2017-07-18

Carbon dioxide (CO 2 ) capture and storage (CCS) is an important climate change mitigation option along with improved energy efficiency, renewable energy, and nuclear energy. CO 2 geosequestration, that is, to store CO 2 under the subsurface of Earth, is feasible because the world's sedimentary basins have high capacity and are often located in the same region of the world as emission sources. How CO 2 interacts with the connate water and minerals is the focus of this Account. There are four trapping mechanisms that keep CO 2 in the pores of subsurface rocks: (1) structural trapping, (2) residual trapping, (3) dissolution trapping, and (4) mineral trapping. The first two are dominated by capillary action, where wettability controls CO 2 and water two-phase flow in porous media. We review state-of-the-art studies on CO 2 /water/mineral wettability, which was found to depend on pressure and temperature conditions, salt concentration in aqueous solutions, mineral surface chemistry, and geometry. We then review some recent advances in mineral trapping. First, we show that it is possible to reproduce the CO 2 /water/mineral wettability at a wide range of pressures using molecular dynamics (MD) simulations. As the pressure increases, CO 2 gas transforms into a supercritical fluid or liquid at ∼7.4 MPa depending on the environmental temperature. This transition leads to a substantial decrease of the interfacial tension between CO 2 and reservoir brine (or pure water). However, the wettability of CO 2 /water/rock systems depends on the type of rock surface. Recently, we investigated the contact angle of CO 2 /water/silica systems with two different silica surfaces using MD simulations. We found that contact angle increased with pressure for the hydrophobic (siloxane) surface while it was almost constant for the hydrophilic (silanol) surface, in excellent agreement with experimental observations. Furthermore, we found that the CO 2 thin films at the CO 2 -hydrophilic

Surface modification of the titanium implant using TEA CO{sub 2} laser pulses in controllable gas atmospheres - Comparative study

Energy Technology Data Exchange (ETDEWEB)

Ciganovic, J.; Stasic, J.; Gakovic, B.; Momcilovic, M.; Milovanovic, D. [VINCA Institute of Nuclear Sciences, University of Belgrade, P.O. BOX 522, 11001 Belgrade (Serbia); Bokorov, M. [Faculty of Sciences, Department of Biology and Ecology, University of Novi Sad, Trg Dositeja Obradovica 3, 21000 Novi Sad (Serbia); Trtica, M., E-mail: etrtica@vinca.rs [VINCA Institute of Nuclear Sciences, University of Belgrade, P.O. BOX 522, 11001 Belgrade (Serbia)

2012-01-15

Interaction of a TEA CO{sub 2} laser, operating at 10.6 {mu}m wavelength and pulse duration of 100 ns (FWHM), with a titanium implant in various gas atmospheres was studied. The Ti implant surface modification was typically studied at the moderate laser beam energy density/fluence of 28 J/cm{sup 2} in the surrounding of air, N{sub 2}, O{sub 2} or He. The energy absorbed from the TEA CO{sub 2} laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following titanium implant surface changes and phenomena were observed, depending on the gas used: (i) creation of cone-like surface structures in the atmospheres of air, N{sub 2} and O{sub 2}, and dominant micro-holes/pores in He ambient; (ii) hydrodynamic features, most prominent in air; (iii) formation of titanium nitride and titanium oxide layers, and (iv) occurrence of plasma in front of the implant. It can be concluded from this study that the reported laser fluence and gas ambiences can effectively be applied for enhancing the titanium implant roughness and creation of titanium oxides and nitrides on the strictly localized surface area. The appearance of plasma in front of the implants indicates relatively high temperatures created above the surface. This offers a sterilizing effect, facilitating contaminant-free conditions.

Decontamination of solid matrices using supercritical CO{sub 2}: study of contaminant-additives-CO{sub 2}; Decontamination de matrices organiques solides par CO{sub 2} supercritique: etude des interactions contaminant-additifs-CO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Galy, J

2006-11-15

This work deals with the decontamination of solid matrices by supercritical CO{sub 2} and more particularly with the study of the interactions between the surfactants and the CO{sub 2} in one part, and with the interactions between the contaminant and the surfactants in another part. The first part of this study has revealed the different interactions between the Pluronics molecules and the supercritical CO{sub 2}. The diagrams graphs have shown that the pluronics (PE 6100, PE 8100 and PE 10100) present a solubility in the supercritical CO{sub 2} low but sufficient (0.1% m/m at 25 MPa and 313 K) for the studied application: the treatment of weak quantities of cerium oxide (or plutonium). An empirical approach based on the evolutions of the slops value and of the origin ordinates of the PT diagrams has been carried out to simulate the phase diagrams PT of the Pluronics. A modeling based on the state equations 'SAFT' (Statistical Associating Fluid Theory) has been studied in order to confirm the experimental results of the disorder points and to understand the role of the different blocks 'PEO' and 'PPO' in the behaviour of Pluronics; this modeling confirms the evolution of the slopes value with the 'CO{sub 2}-phily' of the system. The measure of the surface tension in terms of the Pluronics concentration (PE 6100, 81000 and 10100) has shown different behaviours. For the PE 6100, the surface tension decreases when the surfactant concentration increases (at constant pressure and temperature); on the other hand, for the PE 8100 a slop rupture appears and corresponds to the saturation of the interface water/CO{sub 2} and allows then to determine the Interface Saturation Concentration (ISC). The ISC value (at constant pressure and temperature) increases with an increase of the 'CO{sub 2}-phily'). The model hydrophilous medium being an approximation, it has been replaced by a solid polar phase of CeO{sub 2}. A parallel has

Enhanced the performance of graphene oxide/polyimide hybrid membrane for CO2 separation by surface modification of graphene oxide using polyethylene glycol

Science.gov (United States)

Wu, Li-guang; Yang, Cai-hong; Wang, Ting; Zhang, Xue-yang

2018-05-01

Polyethylene glycol (PEG) with different molecular weights was first used to modify graphene oxide (GO) samples. Subsequently, polyimide (PI) hybrid membranes containing modified-GO were fabricated via in situ polymerization. The separation performance of these hybrid membranes was evaluated using permeation experiments for CO2 and N2 gases. The morphology characterization showed that PEG with suitable molecular weight could be successfully grafted on the GO surface. PEG modification altered the surface properties of GO and introduced defective structures onto GO surface. This caused strong surface polarity and high free volume of membranes containing PEG-modified GO, thereby improving the separation performance of membranes. The addition of PEG-GO with low molecular weight effectively increased gas diffusion through hybrid membranes. The hybrid membranes containing PEG-GO with large molecular weight had high solubility performance for CO2 gas due to the introduction of numerous polar groups into polymeric membranes. With the loading content of modified GO, the CO2 gas permeability of hybrid membranes initially increased but eventually decreased. The optimal content of modified GO in membranes reached 3.0 wt%. When too much PEG added (exceeding 30 g), some impurities formed on GO surface and some aggregates appeared in the resulting hybrid membrane, which depressed the membrane performance.

Wollastonite Carbonation in Water-Bearing Supercritical CO2: Effects of Particle Size.

Science.gov (United States)

Min, Yujia; Li, Qingyun; Voltolini, Marco; Kneafsey, Timothy; Jun, Young-Shin

2017-11-07

The performance of geologic CO 2 sequestration (GCS) can be affected by CO 2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO 2 (scCO 2 ) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO 3 ) at 60 °C and 100 bar in water-bearing scCO 2 . After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO 2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO 2 . The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO 2 .