WorldWideScience

Sample records for catalyzed hydrogen generation

  1. Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

    International Nuclear Information System (INIS)

    The Hanford Waste Vitrification Plant (HWVP) is being designed by the U.S. Department of Energy to immobilize high-level nuclear waste. Simulants for the HWVP feed containing the major nonradioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO32-, NO3- and NO2- were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO2H→H2+/CO2 catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small-scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100 degree C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO2, H2, NO, and N2O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl3.3H2O, was found to be the most active catalyst for hydrogen generation from formic acid above nearly 80 degree C in the presence of nitrite ion in accord with earlier observations. The apparent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is consistent with the approximate pseudo-first-order dependence of the hydrogen production rate on Rh concentration. 24 refs., 7 figs., 2 tabs

  2. Hydrogen evolution catalyzed by cobaloximes.

    Science.gov (United States)

    Dempsey, Jillian L; Brunschwig, Bruce S; Winkler, Jay R; Gray, Harry B

    2009-12-21

    Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H(2)O, CO(2)) to energy-rich ones (O(2), (CH(2)O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the "Holy Grail" of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H(2). In this Account, we report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co(II)-diglyoxime generates a Co(I) species that reacts with a proton source to produce a Co(III)-hydride. Then, in a homolytic pathway, two Co(III)-hydrides react in a bimolecular step to eliminate H(2). Alternatively, in a heterolytic pathway, protonation of the Co(III)-hydride produces H(2) and Co(III). A thermodynamic analysis of H(2) evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co(I)-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H(2) evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co(III)-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H(2) evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co(III)-hydrides. PMID:19928840

  3. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    Science.gov (United States)

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.

    2008-09-16

    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  4. Electrochemical Hydrogen Peroxide Generator

    Science.gov (United States)

    Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

    2010-01-01

    Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials

  5. Transfer Hydrogenation of Acetophenone Catalyzed by in situ Generated 2,6-Bis(5-thioxo-4,5-dihydro-1,2,4-triazole- 3-yl)pyridine-ruthenium(Ⅱ) Complexes

    Institute of Scientific and Technical Information of China (English)

    CETIN,Ahmet; DAYAN,Osman

    2009-01-01

    2,6-Bis(5-thioxo-4,5-dihydro-1,2,4-triazole-3-yl)pyridines (3, 4) were used for the first time as ligand in ruthe-nium catalyzed transfer hydrogenation of acetophenone. The in situ prepared three-component system Ru(ll)/tridentate triamine ligands (3a-3d, 4a-4d) and KOH catalysed the transfer hydrogenation reaction of ace-tophenone in good yields under mild conditions.

  6. Hydrogen storage and generation system

    Science.gov (United States)

    Dentinger, Paul M.; Crowell, Jeffrey A. W.

    2010-08-24

    A system for storing and generating hydrogen generally and, in particular, a system for storing and generating hydrogen for use in an H.sub.2/O.sub.2 fuel cell. The hydrogen storage system uses the beta particles from a beta particle emitting material to degrade an organic polymer material to release substantially pure hydrogen. In a preferred embodiment of the invention, beta particles from .sup.63Ni are used to release hydrogen from linear polyethylene.

  7. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    Science.gov (United States)

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  8. Catalyzed hydrogenation of nitrogen and ethylene on metal (Fe, Pt) single crystal surfaces and effects of coadsorption: A sum frequency generation vibrational spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Westerberg, Staffan Per Gustav

    2004-12-15

    High-pressure catalytic reactions and associated processes, such as adsorption have been studied on a molecular level on single crystal surfaces. Sum Frequency Generation (SFG) vibrational spectroscopy together with Auger Electron Spectroscopy (AES), Temperature Programmed Desorption (TPD) and Gas Chromatography (GC) were used to investigate the nature of species on catalytic surfaces and to measure the catalytic reaction rates. Special attention has been directed at studying high-pressure reactions and in particular, ammonia synthesis in order to identify reaction intermediates and the influence of adsorbates on the surface during reaction conditions. The adsorption of gases N{sub 2}, H{sub 2}, O{sub 2} and NH{sub 3} that play a role in ammonia synthesis have been studied on the Fe(111) crystal surface by sum frequency generation vibrational spectroscopy using an integrated Ultra-High Vacuum (UHV)/high-pressure system. SFG spectra are presented for the dissociation intermediates, NH{sub 2} ({approx}3325 cm{sup -1}) and NH ({approx}3235 cm{sup -1}) under high pressure of ammonia (200 Torr) on the clean Fe(111) surface. Addition of 0.5 Torr of oxygen to 200 Torr of ammonia does not significantly change the bonding of dissociation intermediates to the surface. However, it leads to a phase change of nearly 180{sup o} between the resonant and non-resonant second order non-linear susceptibility of the surface, demonstrated by the reversal of the SFG spectral features. Heating the surface in the presence of 200 Torr ammonia and 0.5 Torr oxygen reduces the oxygen coverage, which can be seen from the SFG spectra as another relative phase change of 180{sup o}. The reduction of the oxide is also supported by Auger electron spectroscopy. The result suggests that the phase change of the spectral features could serve as a sensitive indicator of the chemical environment of the adsorbates.

  9. Hydrogen Generation From Electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Steven Cohen; Stephen Porter; Oscar Chow; David Henderson

    2009-03-06

    Small-scale (100-500 kg H2/day) electrolysis is an important step in increasing the use of hydrogen as fuel. Until there is a large population of hydrogen fueled vehicles, the smaller production systems will be the most cost-effective. Performing conceptual designs and analyses in this size range enables identification of issues and/or opportunities for improvement in approach on the path to 1500 kg H2/day and larger systems. The objectives of this program are to establish the possible pathways to cost effective larger Proton Exchange Membrane (PEM) water electrolysis systems and to identify areas where future research and development efforts have the opportunity for the greatest impact in terms of capital cost reduction and efficiency improvements. System design and analysis was conducted to determine the overall electrolysis system component architecture and develop a life cycle cost estimate. A design trade study identified subsystem components and configurations based on the trade-offs between system efficiency, cost and lifetime. Laboratory testing of components was conducted to optimize performance and decrease cost, and this data was used as input to modeling of system performance and cost. PEM electrolysis has historically been burdened by high capital costs and lower efficiency than required for large-scale hydrogen production. This was known going into the program and solutions to these issues were the focus of the work. The program provided insights to significant cost reduction and efficiency improvement opportunities for PEM electrolysis. The work performed revealed many improvement ideas that when utilized together can make significant progress towards the technical and cost targets of the DOE program. The cell stack capital cost requires reduction to approximately 25% of today’s technology. The pathway to achieve this is through part count reduction, use of thinner membranes, and catalyst loading reduction. Large-scale power supplies are available

  10. Development and industrial application of catalyzer for low-temperature hydrogenation hydrolysis of Claus tail gas

    Directory of Open Access Journals (Sweden)

    Honggang Chang

    2015-10-01

    Full Text Available With the implementation of more strict national environmental protection laws, energy conservation, emission reduction and clean production will present higher requirements for sulfur recovery tail gas processing techniques and catalyzers. As for Claus tail gas, conventional hydrogenation catalyzers are gradually being replaced by low-temperature hydrogenation catalyzers. This paper concentrates on the development of technologies for low-temperature hydrogenation hydrolysis catalyzers, preparation of such catalyzers and their industrial application. In view of the specific features of SO2 hydrogenation and organic sulfur hydrolysis during low-temperature hydrogenation, a new technical process involving joint application of hydrogenation catalyzers and hydrolysis catalyzers was proposed. In addition, low-temperature hydrogenation catalyzers and low-temperature hydrolysis catalyzers suitable for low-temperature conditions were developed. Joint application of these two kinds of catalyzers may reduce the inlet temperatures in the conventional hydrogenation reactors from 280 °C to 220 °C, at the same time, hydrogenation conversion rates of SO2 can be enhanced to over 99%. To further accelerate the hydrolysis rate of organic sulfur, the catalyzers for hydrolysis of low-temperature organic sulfur were developed. In lab tests, the volume ratio of the total sulfur content in tail gas can be as low as 131 × 10−6 when these two kinds of catalyzers were used in a proportion of 5:5 in volumes. Industrial application of these catalyzers was implemented in 17 sulfur recovery tail gas processing facilities of 15 companies. As a result, Sinopec Jinling Petrochemical Company had outstanding application performances with a tail gas discharging rate lower than 77.9 mg/m3 and a total sulfur recovery of 99.97%.

  11. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions.

    Science.gov (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter

    2015-02-17

    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  12. Hydrogen generation from renewable resources

    Energy Technology Data Exchange (ETDEWEB)

    Loges, Bjoern

    2009-09-04

    In this thesis, the hydrogen generation by dehydrogenation of 2-propanol and formic acid as model substances for renewable resources have been studied, which is of importance for hydrogen storage. For the base-assisted dehydrogenation of 2-propanol, a ruthenium diamine catalyst system has been investigated. For the selective decomposition of formic acid to hydrogen and carbon dioxide, a system has been established containing ruthenium catalysts and formic acid amine adducts as substrates. The best catalyst activity and productivity have been achieved with in situ generated ruthenium phosphine catalysts, e.g. [RuCl{sub 2}(benzene)]{sub 2} / dppe (TOF = 900 h{sup -1}, TON = 260,000). The gas evolved has been directly used in fuel cells. Furthermore, the influence of irradiation with visible light has been described for the ruthenium phosphine catalysts. (orig.)

  13. NOx-Catalyzed Gas-Phase Activation of Methane:the Formation of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Chaoxian Xiao; Zhen Yan; Yuan Kou

    2003-01-01

    NOx-catalyzed oxidation of methane without a solid catalyst was investigated, and a hydrogen selectivity of 27% was obtained with an overall methane conversion of 34% and a free O2 concentration of 1.7% at 700 ℃.

  14. Magnetic Mesoporous Palladium Catalyzed Selective Hydrogenation of Sunflower Oil.

    Science.gov (United States)

    Liu, Wei; Tian, Fei; Yu, Jingjing; Bi, Yanlan

    2016-05-01

    In this paper, a novel magnetic mesoporous Pd catalyst is used to catalyse selective hydrogenation of sunflower oil at a mild temperature of 50°C. Effects of reaction temperature, stirring speed, time, catalyst loading and hydrogen pressure on the reaction activity, trans fatty acid (TFA) and stearic acid formation were studied. Under the condition of 3.2 mg Pd/100 g oil, 50°C, 1300 rpm stirring speed and 19.0 atm of H2, the lowest amount of TFA generated during the reaction (IV = 80) was 14.9 ± 0.4% while 11.4 ± 0.4% of stearic acid was produced. And this magnetic Pd-catalyst can be reused easily for at least six times without significant catalyst deactivation, the amount of TFA almost remained unchanged. Moreover, this Pd-catalyst shows a good magnetic separation, which provides a potential method for the facile oil modification. PMID:27086993

  15. Acid-catalyzed hydrogenation of olefins. A theoretical study of the HF- and H/sub 3/O/sup +/-catalyzed hydrogenation of ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Siria, J.C.; Duran, M.; Lledos, A.; Bertran, J.

    1987-12-09

    The HF- and H/sub 3/O/sup +/-catalyzed hydrogenation of ethylene and the direct addition of molecular hydrogen to ethylene have been studied theoretically by means of ab initio MO calculations using different levels of theory. The main results are that catalysis by HF lowers the potential energy barrier to a large extent, while catalysis by H/sub 3/O/sup +/ diminishes dramatically the barrier for the reaction. Entropic contributions leave these results unchanged. The mechanisms of the two acid-catalyzed hydrogenations are somewhat different. While catalysis by HF exhibits bifunctional characteristics, catalysis by H/sub 3/O/sup +/ proceeds via an initial formation of a carbocation. It is shown that catalysis by strong acids may be an alternate way for olefin hydrogenation.

  16. Fuel cell using a hydrogen generation system

    Science.gov (United States)

    Dentinger, Paul M.; Crowell, Jeffrey A. W.

    2010-10-19

    A system is described for storing and generating hydrogen and, in particular, a system for storing and generating hydrogen for use in an H.sub.2/O.sub.2 fuel cell. The hydrogen storage system uses beta particles from a beta particle emitting material to degrade an organic polymer material to release substantially pure hydrogen. In a preferred embodiment of the invention, beta particles from .sup.63Ni are used to release hydrogen from linear polyethylene.

  17. A Step into an eco-Compatible Future: Iron- and Cobalt-catalyzed Borrowing Hydrogen Transformation.

    Science.gov (United States)

    Quintard, Adrien; Rodriguez, Jean

    2016-01-01

    Living on borrowed hydrogen: Recent developments in iron- and cobalt-catalyzed borrowing hydrogen have shown that economically reliable catalysts can be used in this type of waste-free reactions. By using well-defined inexpensive catalysts, known reactions can now be run efficiently without the necessary use of noble metals; however, in addition new types of reactivity can also be discovered.

  18. Hydrogen generation in tru waste transportation packages

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, B; Sheaffer, M K; Fischer, L E

    2000-03-27

    This document addresses hydrogen generation in TRU waste transportation packages. The potential sources of hydrogen generation are summarized with a special emphasis on radiolysis. After defining various TRU wastes according to groupings of material types, bounding radiolytic G-values are established for each waste type. Analytical methodologies are developed for prediction of hydrogen gas concentrations for various packaging configurations in which hydrogen generation is due to radiolysis. Representative examples are presented to illustrate how analytical procedures can be used to estimate the hydrogen concentration as a function of time. Methodologies and examples are also provided to show how the time to reach a flammable hydrogen concentration in the innermost confinement layer can be estimated. Finally, general guidelines for limiting the hydrogen generation in the payload and hydrogen accumulation in the innermost confinement layer are described.

  19. Lipase catalyzed interesterification of rice bran oil with hydrogenated cottonseed oil to produce trans free fat.

    Science.gov (United States)

    Neeharika, T S V R; Rallabandi, Ramya; Ragini, Y; Kaki, Shiva Shanker; Rani, K N Prasanna; Prasad, R B N

    2015-08-01

    Lipase catalyzed interesterification of rice bran oil (RBO) with hydrogenated cottonseed oil (HCSO) was carried out for producing a low trans free fat. The interesterification reaction was performed by varying parameters such as weight proportions of RBO and HCSO, reaction temperatures, time period and lipase concentration. Both non specific and specific lipases namely Novozym 435 and Lipozyme TL IM were employed for this study. Based on the data generated, the optimum reaction conditions were found to be: weight proportion of RBO and HCSO, 80:20; lipase concentration, 5 % (w/w) of substrates; reaction temperature, 60 °C; reaction time, 4 h for Lipozyme TL IM and 5 h for Novozym 435. The degree of interesterification, calculated based on the results of solid fat characteristics was used for comparing the catalytic activity of Novozym 435 and Lipozyme TL IM. It was observed that the degree of interesterification (DI) reached a near 100 % at the 4th hour for reaction employing Lipozyme TL IM with a rate constant of 0.191 h(-1) while Novozym 435 catalyzed reaction reached a near 100 % degree of interesterification at the 5th hour with a rate constant of 0.187 h(-1), suggesting that Lipozyme TL IM has a faster catalytic activity.

  20. Destabilized and catalyzed borohydride for reversible hydrogen storage

    Science.gov (United States)

    Mohtadi, Rana F.; Nakamura, Kenji; Au, Ming; Zidan, Ragaiy

    2012-01-31

    A process of forming a hydrogen storage material, including the steps of: providing a first material of the formula M(BH.sub.4).sub.X, where M is an alkali metal or an alkali earth metal, providing a second material selected from M(AlH.sub.4).sub.x, a mixture of M(AlH.sub.4).sub.x and MCl.sub.x, a mixture of MCl.sub.x and Al, a mixture of MCl.sub.x and AlH.sub.3, a mixture of MH.sub.x and Al, Al, and AlH.sub.3. The first and second materials are combined at an elevated temperature and at an elevated hydrogen pressure for a time period forming a third material having a lower hydrogen release temperature than the first material and a higher hydrogen gravimetric density than the second material.

  1. Solar Fuels. Photocatalytic Hydrogen Generation

    OpenAIRE

    Kamat, Prashant V.; Bisquert, Juan

    2013-01-01

    The necessity for developing clean energy technology has led to the surge in renewable energy research. A major effort is in discovering new approaches for producing transportable fuels. Hydrogen, which possesses the highest energy density (120 MJ/kg) known for any fuel and no carbon footprint, is regarded as the leading contender for meeting future fuel needs. The term Hydrogen Economy is often referred collectively to the topics of production, storage, and transport of hydrogen.

  2. MINERALIZATION OF A SORBED POLYCYCLIC AROMATIC HYDROCARBON IN TWO SOILS USING CATALYZED HYDROGEN PEROXIDE. (R826163)

    Science.gov (United States)

    Hydrogen peroxide (H2O2) catalyzed by soluble iron or naturally occurring soil minerals, (i.e., modified Fenton's reagent) was investigated as a basis for mineralizing sorbed and NAPL-phase benzo[a]pyrene (BaP), a hydrophobic and toxic polycyclic a...

  3. Enantioselective Rh-catalyzed hydrogenation of N-formyl dehydroamino esters with monodentate phosphoramidite ligands

    NARCIS (Netherlands)

    Panella, L; Aleixandre, AM; Kruidhof, GJ; Robertus, J; Feringa, BL; de Vries, JG; Minnaard, AJ; Aleixandre, Alicia Marco; Kruidhof, Gerlof J.; Feringa, Bernard

    2006-01-01

    Enantioselectivities up to > 99% ee were achieved in the rhodium-catalyzed asymmetric hydrogenation of N-formyl dehydroamino esters using morrodentate phosphoramidites as chiral ligands. The substrates were synthesized by condensation of methyl isocyanoacetate with a range of aldehydes and with cycl

  4. Two-chamber hydrogen generation and application: access to pressurized deuterium gas.

    Science.gov (United States)

    Modvig, Amalie; Andersen, Thomas L; Taaning, Rolf H; Lindhardt, Anders T; Skrydstrup, Troels

    2014-06-20

    Hydrogen and deuterium gas were produced and directly applied in a two-chamber system. These gaseous reagents were generated by the simple reaction of metallic zinc with HCl in water for H2 and DCl in deuterated water for D2. The setup proved efficient in classical Pd-catalyzed reductions of ketones, alkynes, alkenes, etc. in near-quantitative yields. The method was extended to the synthesis and isotope labeling of quinoline and 1,2,3,4-tetrahydroquinoline derivatives. Finally, CX-546 and Olaparib underwent efficient Ir-catalyzed hydrogen isotope exchange reactions. PMID:24870212

  5. Gold-catalyzed oxidation of substituted phenols by hydrogen peroxide

    KAUST Repository

    Cheneviere, Yohan

    2010-10-20

    Gold nanoparticles deposited on inorganic supports are efficient catalysts for the oxidation of various substituted phenols (2,6-di-tert-butyl phenol and 2,3,6-trimethyl phenol) with aqueous hydrogen peroxide. By contrast to more conventional catalysts such as Ti-containing mesoporous silicas, which convert phenols to the corresponding benzoquinones, gold nanoparticles are very selective to biaryl compounds (3,3′,5,5′-tetra-tert-butyl diphenoquinone and 2,2′,3,3′,5,5′-hexamethyl-4,4′- biphenol, respectively). Products yields and selectivities depend on the solvent used, the best results being obtained in methanol with yields >98%. Au offers the possibility to completely change the selectivity in the oxidation of substituted phenols and opens interesting perspectives in the clean synthesis of biaryl compounds for pharmaceutical applications. © 2010 Elsevier B.V. All rights reserved.

  6. Asymmetric Hydrogenation of Aromatic Heterocyclic Ketones Catalyzed by the MsDPEN–Cp*Ir(III) Complex

    OpenAIRE

    Utsumi, Noriyuki; Tsutsumi, Kunihiko; Watanabe, Masahiko; Murata, Kunihiko; Arai, Noriyoshi; Kurono, Nobuhito; Ohkuma, Takeshi

    2010-01-01

    Asymmetric hydrogenation of aromatic heterocyclic ketones catalyzed by Cp*Ir(OTf)(Msdpen) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the heterocyclic alcohols in 93% to > 99% ee. The reaction is conducted in a methanolic solution with a substrate-to-catalyst molar ratio of 200-5000 under 15 atm of H2. The heterocyclic rings of substrates are left intact.

  7. Oxidation of chlorophenols catalyzed by Coprinus cinereus peroxidase with in situ production of hydrogen peroxide.

    Science.gov (United States)

    Pezzotti, Fabio; Okrasa, Krzysztof; Therisod, Michel

    2004-01-01

    Degradation of 2,6-dichlorophenol (2,6-DCP) was accomplished by oxidation catalyzed by Coprinus cinereus peroxidase. Immobilization of the enzyme in a polyacrylamide matrix enhanced DCP oxidation. Hydrogen peroxide, peroxidase's natural substrate, was produced enzymatically in situ to avoid peroxidase inactivation by its too high concentration. In the case of larger scale utilization, the method would also avoid direct handling of this hazardous reagent.

  8. Hydrogen dilution effect on microstructure of Si thin film grown by catalyzer enhanced chemical vapor deposition

    International Nuclear Information System (INIS)

    The effect of hydrogen dilution on microstructure of in situ polycrystalline Si (poly-Si) films grown by catalyzer-enhanced chemical vapor deposition (CECVD) has been investigated by using transmission electron microscopy (TEM) and transmission electron diffraction (TED) analysis. It was shown that the increase of the hydrogen dilution ratio resulted in transition of microstructure of Si thin film from amorphous to polycrystalline in CECVD at low substrate temperature (∼80 deg. C). These results indicate that the CECVD technique is a promising candidate to grow high-quality in situ polycrystalline Si films on glass or a flexible substrate for low-temperature poly-Si (LTPS) and flexible displays

  9. Hydrogen dilution effect on microstructure of Si thin film grown by catalyzer enhanced chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Han-Ki [School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology (KIT), 1 Yangho-dong, Gumi, Gyeongbuk, 730-701 (Korea, Republic of)]. E-mail: hkkim@kumoh.ac.kr

    2006-12-15

    The effect of hydrogen dilution on microstructure of in situ polycrystalline Si (poly-Si) films grown by catalyzer-enhanced chemical vapor deposition (CECVD) has been investigated by using transmission electron microscopy (TEM) and transmission electron diffraction (TED) analysis. It was shown that the increase of the hydrogen dilution ratio resulted in transition of microstructure of Si thin film from amorphous to polycrystalline in CECVD at low substrate temperature ({approx}80 deg. C). These results indicate that the CECVD technique is a promising candidate to grow high-quality in situ polycrystalline Si films on glass or a flexible substrate for low-temperature poly-Si (LTPS) and flexible displays.

  10. Hydrogen Generation from Plasmatron Reforming Ethanol

    Institute of Scientific and Technical Information of China (English)

    YOU Fu-bing; HU You-ping; LI Ge-sheng; GAO Xiao-hong

    2006-01-01

    Hydrogen generation through plasmatron reforming of ethanol has been carried out in a dielectric barrier discharge (DBD) reactor. The reforming of pure ethanol and mixtures of ethanol-water have been studied. The gas chromatography (GC) analysis has shown that in all conditions the reforming yield was H2, CO, CH4 and CO2 as the main products, and with little C2* . The hydrogen-rich gas can be used as fuel for gasoline engine and other applications.

  11. A new type of hydrogen generator-HHEG (high-compressed hydrogen energy generator)

    International Nuclear Information System (INIS)

    'Full text:' We have developed a new type of hydrogen generator named HHEG (High-compressed Hydrogen Energy Generator). HHEG can produce 35 MPa high-compressed hydrogen for fuel cell vehicle without any mechanical compressor. HHEG is a kind of PEM(proton exchange membrane)electrolysis. It was well known that compressed hydrogen could be generated by water electrolysis. However, the conventional electrolysis could not generate 35 MPa or higher pressure that is required for fuel cell vehicle, because electrolysis cell stack is destroyed in such high pressure. In HHEG, the cell stack is put in high-pressure vessel and the pressure difference of oxygen and hydrogen that is generated by the cell stack is always kept at nearly zero by an automatic compensator invented by Mitsubishi Corporation. The cell stack of HHEG is not so special one, but it is not broken under such high pressure, because the automatic compensator always offsets the force acting on the cell stack. Hydrogen for fuel cell vehicle must be produce by no emission energy such as solar and atomic power. These energies are available as electricity. So, water electrolysis is the only way of producing hydrogen fuel. Hydrogen fuel is also 35 MPa high-compressed hydrogen and will become 70 MPa in near future. But conventional mechanical compressor is not useful for such high pressure hydrogen fuel, because of the short lifetime and high power consumption. Construction of hydrogen station network is indispensable in order to come into wide use of fuel cell vehicles. For such network contraction, an on-site type hydrogen generator is required. HHEG can satisfy above these requirements. So we can conclude that HHEG is the only way of realizing the hydrogen economy. (author)

  12. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect.

  13. GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II

    Science.gov (United States)

    Green Catalyzed Oxidation of Hydrocarbons in Alternative Solvent Systems Generated by PARIS IIMichael A. Gonzalez*, Thomas M. Becker, and Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26...

  14. Efficient Method for the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Sweeney, William; Lee, James; Abid, Nauman; DeMeo, Stephen

    2014-01-01

    An experiment is described that determines the activation energy (E[subscript a]) of the iodide-catalyzed decomposition reaction of hydrogen peroxide in a much more efficient manner than previously reported in the literature. Hydrogen peroxide, spontaneously or with a catalyst, decomposes to oxygen and water. Because the decomposition reaction is…

  15. HYDROGENATION OF PHENOL AND CRESOLS CATALYZED BY CHITOSAN SUPPORTED PALLADIUM COMPLEX AT MILD CONDITIONS

    Institute of Scientific and Technical Information of China (English)

    TANG Liming; HUANG Meiyu; JIANG Yingyan

    1996-01-01

    A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70℃ and 1.01325 × 105 Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->ocresol. The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.

  16. Environmentally Benign Oxidation of Some Organic Sulfides with 34% Hydrogen Peroxide Catalyzed by Simple Heteropolyoxometalates

    Institute of Scientific and Technical Information of China (English)

    TAYEBEE,Reza; ALIZADEH,Moharnmad Hassan

    2007-01-01

    An environmentally benign oxygenation protocol was developed for selective oxidation of some types of aromatic and aliphatic sulfides in good to excellent yields utilizing 34% hydrogen peroxide catalyzed by simple heteropolyoxometalates in normal drinking water at room temperature. The catalysts could be recovered and reused for at least seven reaction cycles under the described reaction conditions without considerable loss of reactivity. This procedure introduced a new insight into the use of simple heteropolyanions as recoverable catalysts for the oxidation of organic sulfides by an environmentally acceptable protocol.

  17. Catalyzed light hydride nanomaterials embedded in a micro-channels hydrogen storage container.

    Science.gov (United States)

    Dehouche, Zahir; Peretti, Hernán A; Yoo, Yeong; Belkacemi, Khaled; Goyette, Jacques

    2009-01-01

    Activated alloys synthesized by arc-melting were examined as catalysts for improving the hydrogen sorption characteristics of nanostructured magnesium hydride, proposed as a reversible hydrogen storage material. The MgH(2)-catalyst absorbing materials were prepared by ball milling of pure MgH(2) with hydrided Zr(47)Ni(53), Zr(9)Ni(11), and other alloys investigated. The nanostructured MgH(2)-intermetallic systems were tested at 250 degrees C and catalyst addition of eutectoid Zr(47)Ni(53) resulted in the fastest desorption time and highest initial desorption rate. The catalyzed Mg-hydride with activated Zr(9)Ni(11) and Zr(7)Ni(10) phases showed fast desorption kinetics. Moreover, the results demonstrated that the composition of dispersed Zr(x)Ni(y)catalysts has a strong influence on the amount of accumulated hydrogen and desorption rate of Mg-nanocomposite. Part two covers advanced micro-channels hydrogen storage module design based on the results of semi-empirical computer simulations of heat and mass transfers in the container. The micro-channels reservoir concept offers many advantages over the conventional metal hydride hydrogen storage system. It is a micro-structured system that can pack a lot of power into a small space and dissipate effectively the heat of the sorption reactions. This review summarizes recent patents related to CNTS.

  18. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

    Science.gov (United States)

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies. PMID:27441240

  19. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

    Science.gov (United States)

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  20. PipPhos and MorfPhos : Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Bernsmann, Heiko; van den Berg, M; Hoen, Robert; Minnaard, AJ; Mehler, G; Reetz, MT; De Vries, JG; Feringa, BL

    2005-01-01

    A library of 20 monodentate phosphoramidite ligands has been prepared and applied in rhodium-catalyzed asymmetric hydrogenation. This resulted in the identification of two ligands, PipPhos and MorfPhos, that afford excellent and in several cases unprecedented enantioselectivities in the hydrogenatio

  1. HIGH EFFICIENCY GENERATION OF HYDROGEN FUELS USING NUCLEAR POWER

    Energy Technology Data Exchange (ETDEWEB)

    BROWN,LC; BESENBRUCH,GE; LENTSCH,RD; SCHULTZ,KR; FUNK,JF; PICKARD,PS; MARSHALL,AC; SHOWALTER,SK

    2003-06-01

    fossil fuels has trace contaminants (primarily carbon monoxide) that are detrimental to precious metal catalyzed fuel cells, as is now recognized by many of the world's largest automobile companies. Thermochemical hydrogen will not contain carbon monoxide as an impurity at any level. Electrolysis, the alternative process for producing hydrogen using nuclear energy, suffers from thermodynamic inefficiencies in both the production of electricity and in electrolytic parts of the process. The efficiency of electrolysis (electricity to hydrogen) is currently about 80%. Electric power generation efficiency would have to exceed 65% (thermal to electrical) for the combined efficiency to exceed the 52% (thermal to hydrogen) calculated for one thermochemical cycle. Thermochemical water-splitting cycles have been studied, at various levels of effort, for the past 35 years. They were extensively studied in the late 70s and early 80s but have received little attention in the past 10 years, particularly in the U.S. While there is no question about the technical feasibility and the potential for high efficiency, cycles with proven low cost and high efficiency have yet to be developed commercially. Over 100 cycles have been proposed, but substantial research has been executed on only a few. This report describes work accomplished during a three-year project whose objective is to ''define an economically feasible concept for production of hydrogen, by nuclear means, using an advanced high temperature nuclear reactor as the energy source.'' The emphasis of the first phase was to evaluate thermochemical processes which offer the potential for efficient, cost-effective, large-scale production of hydrogen from water in which the primary energy input is high temperature heat from an advanced nuclear reactor and to select one (or, at most three) for further detailed consideration. During Phase 1, an exhaustive literature search was performed to locate all cycles

  2. Treatment of four biorefractory contaminants in soils using catalyzed hydrogen peroxide

    International Nuclear Information System (INIS)

    The treatment of soil with pentachlorophenol, trifluralin, hexadecane, and dieldrin using catalyzed hydrogen peroxide [H2O and iron(II)] was investigated in a soil of low development with organic C ranging from 2,000 mg kg-1 to 16,000 mg kg-1. Soil treatment was conducted at pH 3 with 240 and 400 mg L-1 iron additions and 120,000 mg L-1 H2O2. Pentachlorophenol and trifluralin degradation rates decreased as a function of soil organic C content. However, soil organic C had no effect on the degradation rates of dieldrin and hexadecane. In addition, the four contaminant degraded at equal rates with soil containing organic C > 10,000 mg kg-1. The ratio of first-order rate constant for contaminant degradation to hydrogen peroxide consumption was used as an empirical measure of treatment efficiency. These ratios were sensitive to both the soil and organic C content and to the concentration of iron added during treatment. The efficiency ratios were highest for treatment with no iron addition; these data suggest that iron minerals and H2O2 provide a system in which Fenton-like oxidations pentachlorophenol was evaluated in goethite-, hematite-, and magnetite-silica sand at pH 3. Pentachlorophenol was degraded in the mineral-silica sand systems

  3. ESR ST study of hydroxyl radical generation in wet peroxide system catalyzed by heterogeneous ruthenium

    NARCIS (Netherlands)

    Rokhina, E.V.; Golovina, E.A.; As, van H.; Virkutyte, J.

    2009-01-01

    Ru-based catalysts gained popularity because of their applicability for a variety of processes, including carbon monoxide oxidation, wet air catalytic oxidation and wastewater treatment. The focus of a current study was generation of hydroxyl radicals in the wet peroxide system catalyzed by heteroge

  4. Prion-derived copper-binding peptide fragments catalyze the generation of superoxide anion in the presence of aromatic monoamines

    Directory of Open Access Journals (Sweden)

    Tomonori Kawano

    2007-01-01

    Full Text Available Objectives: Studies have proposed two opposing roles for copper-bound forms of prion protein (PrP as an anti-oxidant supporting the neuronal functions and as a pro-oxidant leading to neurodegenerative process involving the generation of reactive oxygen species. The aim of this study is to test the hypothesis in which putative copper-binding peptides derived from PrP function as possible catalysts for monoamine-dependent conversion of hydrogen peroxide to superoxide in vitro. Materials and methods: Four peptides corresponding to the copper (II-binding motifs in PrP were synthesized and used for analysis of peptide-catalyzed generation of superoxide in the presence of Cu (II and other factors naturally present in the neuronal tissues. Results: Among the Cu-binding peptides tested, the amino acid sequence corresponding to the Cu-binding site in the helical region was shown to be the most active for superoxide generation in the presence of Cu(II, hydrogen peroxide and aromatic monoamines, known precursors or intermediates of neurotransmitters. Among monoamines tested, three compounds namely phenylethylamine, tyramine and benzylamine were shown to be good substrates for superoxide-generating reactions by the Cu-bound helical peptide. Conclusions: Possible roles for these reactions in development of prion disease were suggested.

  5. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

    Full Text Available Complex hydride systems for hydrogen (H2 generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4 with the following additives: nanoiron (n-Fe, lithium amide (LiNH2 (a hydride/hydride system and manganese chloride MnCl2 (a hydride/halide system. Another hydride/hydride system consists of lithium amide (LiNH2 and magnesium hydride (MgH2, and finally, there is a LiBH4-FeCl2 (hydride/halide system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C. In this group lithium alanate (LiAlH4 ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH42 obtained by mechano-chemical activation synthesis (MCAS. In a ball milled (2LiBH4 + MnCl2 nanocomposite, Mn(BH42 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.

  6. Double heterojunction nanowire photocatalysts for hydrogen generation

    Science.gov (United States)

    Tongying, P.; Vietmeyer, F.; Aleksiuk, D.; Ferraudi, G. J.; Krylova, G.; Kuno, M.

    2014-03-01

    Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core

  7. Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

    Science.gov (United States)

    Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

    2016-08-01

    The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

  8. Rate-Enhancing Roles of Water Molecules in Methyltrioxorhenium-Catalyzed Olefin Epoxidation by Hydrogen Peroxide.

    Science.gov (United States)

    Goldsmith, Bryan R; Hwang, Taeho; Seritan, Stefan; Peters, Baron; Scott, Susannah L

    2015-08-01

    Olefin epoxidation catalyzed by methyltrioxorhenium (MTO, CH3ReO3) is strongly accelerated in the presence of H2O. The participation of H2O in each of the elementary steps of the catalytic cycle, involving the formation of the peroxo complexes (CH3ReO2(η(2)-O2), A, and CH3ReO(η(2)-O2)2(H2O), B), as well as in their subsequent epoxidation of cyclohexene, was examined in aqueous acetonitrile. Experimental measurements demonstrate that the epoxidation steps exhibit only weak [H2O] dependence, attributed by DFT calculations to hydrogen bonding between uncoordinated H2O and a peroxo ligand. The primary cause of the observed H2O acceleration is the strong co-catalytic effect of water on the rates at which A and B are regenerated and consequently on the relative abundances of the three interconverting Re-containing species at steady state. Proton transfer from weakly coordinated H2O2 to the oxo ligands of MTO and A, resulting in peroxo complex formation, is directly mediated by solvent H2O molecules. Computed activation parameters and kinetic isotope effects, in combination with proton-inventory experiments, suggest a proton shuttle involving one or (most favorably) two H2O molecules in the key ligand-exchange steps to form A and B from MTO and A, respectively.

  9. Interconversion between formate and hydrogen carbonate by tungsten-containing formate dehydrogenase-catalyzed mediated bioelectrocatalysis

    Directory of Open Access Journals (Sweden)

    Kento Sakai

    2015-09-01

    Full Text Available We have focused on the catalytic properties of tungsten-containing formate dehydrogenase (FoDH1 from Methylobacterium extorquens AM1 to construct a bioelectrochemical interconversion system between formate (HCOO− and hydrogen carbonate (HCO3−. FoDH1 catalyzes both of the HCOO oxidation and the HCO3− reduction with several artificial dyes. The bi-molecular reaction rate constants between FoDH1 and the artificial electron acceptors and NAD+ (as the natural electron acceptor show the property called a linear free energy relationship (LFER, indicating that FoDH1 would have no specificity to NAD+. Similar LFER is also observed for the catalytic reduction of HCO3−. The reversible reaction between HCOO− and HCO3− through FoDH1 has been realized on cyclic voltammetry by using methyl viologen (MV as a mediator and by adjusting pH from the thermodynamic viewpoint. Potentiometric measurements have revealed that the three redox couples, MV2+/MV·−+, HCOO−/HCO3−, FoDH1 (ox/red, reach an equilibrium in the bulk solution when the two-way bioelectrocatalysis proceeds in the presence of FoDH1 and MV. The steady-state voltammograms with two-way bioelectrocatalytic properties are interpreted on a simple model by considering the solution equilibrium.

  10. Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine- Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    HU Juan, WANG Dao-yong, ZHENG Zhuo, HU Xiang-ping J. Mol. Catal. (China) 2012, 26(6), 487 ~492 Chiral phosphine-phosphoramidite ligand, ( So, S,, )-2b, was found to be highly efficient in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates, in which excellent enantioselectivities (up to 〉99% ee) and high catalyticactivity ( S/C up to 5000) were achieved.

  11. Tryptophanase-Catalyzed l-Tryptophan Synthesis from d-Serine in the Presence of Diammonium Hydrogen Phosphate

    OpenAIRE

    Fujii Noriko; Haruka Ozaki; Takeshi Saito; Akihiko Shimada

    2009-01-01

    Tryptophanase, an enzyme with extreme absolute stereospecificity for optically active stereoisomers, catalyzes the synthesis of L-tryptophan from L-serine and indole through a β-substitution mechanism of the ping-pong type, and has no activity on D-serine. We previously reported that tryptophanase changed its stereospecificity to degrade D-tryptophan in highly concentrated diammonium hydrogen phosphate, (NH4)2HPO4 solution. The present study provided the same stereospecific change seen in the...

  12. Tryptophanase-Catalyzed l-Tryptophan Synthesis from d-Serine in the Presence of Diammonium Hydrogen Phosphate

    OpenAIRE

    Shimada, Akihiko; Ozaki, Haruka; Saito, Takeshi; Fujii, Noriko

    2009-01-01

    Tryptophanase, an enzyme with extreme absolute stereospecificity for optically active stereoisomers, catalyzes the synthesis of l-tryptophan from l-serine and indole through a β-substitution mechanism of the ping-pong type, and has no activity on d-serine. We previously reported that tryptophanase changed its stereospecificity to degrade d-tryptophan in highly concentrated diammonium hydrogen phosphate, (NH4)2HPO4 solution. The present study provided the same stereospecific change seen in the...

  13. Generating single-photon catalyzed coherent states with quantum-optical catalysis

    Science.gov (United States)

    Xu, Xue-xiang; Yuan, Hong-chun

    2016-07-01

    We theoretically generate single-photon catalyzed coherent states (SPCCSs) by means of quantum-optical catalysis based on the beam splitter (BS) or the parametric amplifier (PA). These states are obtained in one of the BS (or PA) output channels if a coherent state and a single-photon Fock state are present in two input ports and a single photon is registered in the other output port. The success probabilities of the detection (also the normalization factors) are discussed, which is different for BS and PA catalysis. In addition, we prove that the generated states catalyzed by BS and PA devices are actually the same quantum states after analyzing photon number distribution of the SPCCSs. The quantum properties of the SPCCSs, such as sub-Poissonian distribution, anti-bunching effect, quadrature squeezing effect, and the negativity of the Wigner function are investigated in detail. The results show that the SPCCSs are non-Gaussian states with an abundance of nonclassicality.

  14. IDCOR approach to hydrogen generation, combustion, and burn control

    International Nuclear Information System (INIS)

    The IDCOR Program is developing the appropriate information and methodology to predict the following phenomena during severe accidents: 1) hydrogen generation, both in-vessel and ex-vessel, primarily from metal-water reactions; 2) hydrogen distribution in reactor containments; and 3) potential hazards of overpressurization or combustion of hydrogen. The information is being assembled into reports describing the phenomenology and incorporated into the IDCOR Modular Accident Analysis Program, in order to determine the behavior of hydrogen during accident sequences on four reference plants. From these analyses, conditions will be determined so that hydrogen burn control measures can be evaluated. A review is being made of various approaches for suppression of combustion or controlled burning to limit hydrogen to concentrations below the detonation range. The review considers the advantages and disadvantages of various hydrogen control systems concepts for reactor and containment combinations and, in addition, addresses the various concepts for eventual removal of hydrogen from containment

  15. Catalyzed Nano-Framework Stablized High Density Reversible Hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xia [value too long for type character varying(50); Opalka, Susanne M.; Mosher, Daniel A; Laube, Bruce L; Brown, Ronald J; Vanderspurt, Thomas H; Arsenault, Sarah; Wu, Robert; Strickler, Jamie; Ronnebro, Ewa; Boyle, Tim; Cordaro, Joseph

    2010-06-30

    A wide range of high capacity on-board rechargeable material candidates have exhibited non-ideal behavior related to irreversible hydrogen discharge / recharge behavior, and kinetic instability or retardation. This project addresses these issues by incorporating solvated and other forms of complex metal hydrides, with an emphasis on borohydrides, into nano-scale frameworks of low density, high surface area skeleton materials to stabilize, catalyze, and control desorption product formation associated with such complex metal hydrides. A variety of framework chemistries and hydride / framework combinations were investigated to make a relatively broad assessment of the method's potential. In this project, the hydride / framework interactions were tuned to decrease desorption temperatures for highly stable compounds or increase desorption temperatures for unstable high capacity compounds, and to influence desorption product formation for improved reversibility. First principle modeling was used to explore heterogeneous catalysis of hydride reversibility by modeling H2 dissociation, hydrogen migration, and rehydrogenation. Atomic modeling also demonstrated enhanced NaTi(BH4)4 stabilization at nano-framework surfaces modified with multi-functional agents. Amine multi-functional agents were found to have more balanced interactions with nano-framework and hydride clusters than other functional groups investigated. Experimentation demonstrated that incorporation of Ca(BH4)2 and Mg(BH4)2 in aerogels enhanced hydride desorption kinetics. Carbon aerogels were identified as the most suitable nano-frameworks for hydride kinetic enhancement and high hydride loading. High loading of NaTi(BH4)4 ligand complex in SiO2 aerogel was achieved and hydride stability was improved with the aerogel. Although improvements of desorption kinetics was observed, the incorporation of

  16. Semi-catalyzed deuterium reactors for co-generation of 3He and synfuels (the CoSCD concept)

    International Nuclear Information System (INIS)

    The potential of developing semi-catalyzed deuterium reactors for co-generation of 3He and synthetic fuels is discussed. Such factors as environmental impact, siting, energy basics, and engineering technology are also discussed

  17. On-site hydrogen generation from biodiesel and diesel

    OpenAIRE

    Martin, Stefan

    2015-01-01

    The lack of hydrogen infrastructure and distribution poses an obstacle for the introduction of fuel cell vehicles to the market. Therefore it is reasonable to consider using liquid fuels for on-board or on-site hydrogen generation. Within the FP7 project NEMESIS2+ (01/2012-06/2015, www.nemesis-project.eu) a small-scale hydrogen generator capable of producing 50 Nm3h-1 from biodiesel and diesel is currently being developed. Reduction of hydrogen production costs (< 5.0 € per kg), high overall...

  18. Selective conversion of polyenes to monoenes by RuCl(3) -catalyzed transfer hydrogenation: the case of cashew nutshell liquid.

    Science.gov (United States)

    Perdriau, Sébastien; Harder, Sjoerd; Heeres, Hero J; de Vries, Johannes G

    2012-12-01

    Cardanol, a constituent of cashew nutshell liquid (CNSL), was subjected to transfer hydrogenation catalyzed by RuCl(3) using isopropanol as a reductant. The side chain of cardanol, which is a mixture of a triene, a diene, and a monoene, was selectively reduced to the monoene. Surprisingly, it is the C8-C9 double bond that is retained with high selectivity. A similar transfer hydrogenation of linoleic acid derivatives succeeded only if the substrate contained an aromatic ring, such as a benzyl ester. TEM and a negative mercury test showed that the catalyst was homogeneous. By using ESI-MS, ruthenium complexes were identified that contained one, two, or even three molecules of substrate, most likely as allyl complexes. The interaction between ruthenium and the aromatic ring determines selectivity in the hydrogenation reaction. PMID:23060315

  19. A Study of Hydrogen Generation with Doubly-Fed Adjustable Speed Wind Generator

    Science.gov (United States)

    Kinoshita, Hirotaka; Takahashi, Rion; Murata, Toshiaki; Tamura, Junji; Sugimasa, Masatoshi; Komura, Akiyoshi; Futami, Motoo; Ichinose, Masaya; Ide, Kazumasa

    This paper presents a combination system of wind power generator and hydrogen generator. In the proposed system, Doubly-Fed Synchronous Generator (DFSG) is used as an adjustable speed wind generator, and an electrolyzer is connected to its terminal for hydrogen generation, which is controlled by power electronic converters. Output power from the wind generator is smoothed and supplied to the power system as well as to the electrolyzer to generate hydrogen under a cooperative control of the wind generator and the electrolyzer. The performance of the proposed system is investigated by simulation analyses, in which simulations are performed by using PSCAD/EMTDC.

  20. Formic Acid Free Flowsheet Development To Eliminate Catalytic Hydrogen Generation In The Defense Waste Processing

    Energy Technology Data Exchange (ETDEWEB)

    Lambert, Dan P.; Stone, Michael E.; Newell, J. David; Fellinger, Terri L.; Bricker, Jonathan M.

    2012-09-14

    The Defense Waste Processing Facility (DWPF) processes legacy nuclear waste generated at the Savannah River Site (SRS) during production of plutonium and tritium demanded by the Cold War. The nuclear waste is first treated via a complex sequence of controlled chemical reactions and then vitrified into a borosilicate glass form and poured into stainless steel canisters. Converting the nuclear waste into borosilicate glass canisters is a safe, effective way to reduce the volume of the waste and stabilize the radionuclides. Testing was initiated to determine whether the elimination of formic acid from the DWPF's chemical processing flowsheet would eliminate catalytic hydrogen generation. Historically, hydrogen is generated in chemical processing of alkaline High Level Waste sludge in DWPF. In current processing, sludge is combined with nitric and formic acid to neutralize the waste, reduce mercury and manganese, destroy nitrite, and modify (thin) the slurry rheology. The noble metal catalyzed formic acid decomposition produces hydrogen and carbon dioxide. Elimination of formic acid by replacement with glycolic acid has the potential to eliminate the production of catalytic hydrogen. Flowsheet testing was performed to develop the nitric-glycolic acid flowsheet as an alternative to the nitric-formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be reduced and removed by steam stripping in DWPF with no catalytic hydrogen generation. All processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Ten DWPF tests were performed with nonradioactive simulants designed to cover a broad compositional range. No hydrogen was generated in testing without formic acid.

  1. Hydrogen-based power generation from bioethanol steam reforming

    International Nuclear Information System (INIS)

    This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO2 emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint

  2. Hydrogen-based power generation from bioethanol steam reforming

    Energy Technology Data Exchange (ETDEWEB)

    Tasnadi-Asztalos, Zs., E-mail: tazsolt@chem.ubbcluj.ro; Cormos, C. C., E-mail: cormos@chem.ubbcluj.ro; Agachi, P. S. [Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, 11 Arany Janos, Postal code: 400028, Cluj-Napoca (Romania)

    2015-12-23

    This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO{sub 2} emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint.

  3. Hydrogen-based power generation from bioethanol steam reforming

    Science.gov (United States)

    Tasnadi-Asztalos, Zs.; Cormos, C. C.; Agachi, P. S.

    2015-12-01

    This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO2 emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint.

  4. On-site production of electrolytic hydrogen for generator cooling

    Science.gov (United States)

    Mehta, B. R.

    Hydrogen produced by water electrolysis could be cost effective over the merchant hydrogen used for generator cooling. Advanced water electrolyzers are being developed specifically for this utility application. These designs are based on solid-polymer-electrolyte and alkaline water electrolysis technologies. This paper describes the status of electrolyzer development and demonstration projects.

  5. Efficient Electrochemical Hydrogen Peroxide Generation in Water Project

    Data.gov (United States)

    National Aeronautics and Space Administration — An electrochemical cell is proposed for the efficient generation of 3% hydrogen peroxide (H2O2) in pure water using only power, oxygen and water. H2O2 is an...

  6. Cold weather hydrogen generation system and method of operation

    Energy Technology Data Exchange (ETDEWEB)

    Dreier, Ken Wayne (Madison, CT); Kowalski, Michael Thomas (Seymour, CT); Porter, Stephen Charles (Burlington, CT); Chow, Oscar Ken (Simsbury, CT); Borland, Nicholas Paul (Montpelier, VT); Goyette, Stephen Arthur (New Hartford, CT)

    2010-12-14

    A system for providing hydrogen gas is provided. The system includes a hydrogen generator that produces gas from water. One or more heat generation devices are arranged to provide heating of the enclosure during different modes of operation to prevent freezing of components. A plurality of temperature sensors are arranged and coupled to a controller to selectively activate a heat source if the temperature of the component is less than a predetermined temperature.

  7. Studies on the Epoxidation of Styrene with Hydrogen Peroxide Catalyzed by MCM-41 Supported Co(II) Phenanthroline Complex

    Institute of Scientific and Technical Information of China (English)

    LOU; JianFang

    2001-01-01

    The epoxide is a kind of versatile intermediate for manufacture of a wide variety of fine chemicals. The goal of modem efficient catalytic methods is to produce desired compounds with high yield, selectivity, low cost, safety, operational simplicity and more importantly environmentally benign manner. However, there are various oxidants, which are often hazardous or expensive, being used for both laboratory and industrial epoxidation. Hydrogen peroxide (30 wt%) solution is thought as one of the ideal oxidants because water is a sole theoretical side product. Meanwhile the epoxidation of styrene is a typical one among olefins. Here, the performance of styrene epoxidation was studied with hydrogen peroxide solution catalyzed by Co(Ⅱ) phenanthroline complex encapsulated in supercages of MCM-41.  ……

  8. Hydrogenation of Olefins Catalyzed by Highly Active Titanocene/NaH or n-BuLi Catalyst Systems

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The effects of the substituents on the cyclopentadienyl ring and the reducing agents on the catalytic activity and the stability of titanocene/NaH or n-BuLi systems for the hydrogenation of olefins were investigated. For the catalyst systems composed of titanocene/NaH or n-BuLi, the nature and the number of the substituents on the cyclopentadienyl ring control the catalytic behavior of those two systems. The effect of the reducing agent on the catalytic activity is relatively small. In addition, the characters of the hydrogenation of various olefins catalyzed respectively by Cp2TiCl2/NaH or n-BuLi systems were compared.

  9. Tryptophanase-catalyzed L-tryptophan synthesis from D-serine in the presence of diammonium hydrogen phosphate.

    Science.gov (United States)

    Shimada, Akihiko; Ozaki, Haruka; Saito, Takeshi; Noriko, Fujii

    2009-06-01

    Tryptophanase, an enzyme with extreme absolute stereospecificity for optically active stereoisomers, catalyzes the synthesis of l-tryptophan from l-serine and indole through a beta-substitution mechanism of the ping-pong type, and has no activity on d-serine. We previously reported that tryptophanase changed its stereospecificity to degrade d-tryptophan in highly concentrated diammonium hydrogen phosphate, (NH(4))(2)HPO(4) solution. The present study provided the same stereospecific change seen in the d-tryptophan degradation reaction also occurs in tryptophan synthesis from d-serine. Tryptophanase became active to d-serine to synthesize l-tryptophan in the presence of diammonium hydrogen phosphate. This reaction has never been reported before. d-serine seems to undergo beta-replacement via an enzyme-bonded alpha-aminoacylate intermediate to yield l-tryptophan.

  10. Studies on the Epoxidation of Styrene with Hydrogen Peroxide Catalyzed by MCM-41 Supported Co(II) Phenanthroline Complex

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ The epoxide is a kind of versatile intermediate for manufacture of a wide variety of fine chemicals. The goal of modem efficient catalytic methods is to produce desired compounds with high yield, selectivity, low cost, safety, operational simplicity and more importantly environmentally benign manner. However, there are various oxidants, which are often hazardous or expensive, being used for both laboratory and industrial epoxidation. Hydrogen peroxide (30 wt%) solution is thought as one of the ideal oxidants because water is a sole theoretical side product. Meanwhile the epoxidation of styrene is a typical one among olefins. Here, the performance of styrene epoxidation was studied with hydrogen peroxide solution catalyzed by Co(Ⅱ) phenanthroline complex encapsulated in supercages of MCM-41.

  11. Study on Kinetics of Hydrogen Absorption by Metal Hydride Slurries Ⅱ. Hydrogenation of Benzene Catalyzed by MlNi5

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

    The feasibility of the hydrogenation of benzene into cyclohexane over the hydrogen storage alloy MlNi5 catalyst was studied in the temperature range of 402~463 K. The results show that the reaction order is zero and the energy of activation is 28.9 kJmol-1.

  12. Alkali free hydrolysis of sodium borohydride for hydrogen generation under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, M.J.F.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto (Portugal); Gales, L. [Instituto de Biologia Molecular e Celular, Universidade do Porto, Rua do Campo Alegre 823, 4150-180 Porto and Instituto de Ciencias Biomedicas Abel Salazar, Largo Prof. Abel Salazar 2, 4099-003 Porto (Portugal); Fernandes, V.R.; Rangel, C.M. [Laboratorio Nacional de Energia e Geologia - LNEG, Fuel Cells and Hydrogen Unit Estrada do Paco do Lumiar 22, 1649-038 Lisboa (Portugal)

    2010-09-15

    The present study is related with the production of hydrogen gas (H{sub 2}), at elevated pressures and with high gravimetric storage density, to supply a PEM fuel cell on-demand. To achieve this goal, solid sodium borohydride (NaBH{sub 4}) was mixed with a proper amount of a powder reused nickel-ruthenium based catalyst (Ni-Ru based/NaBH{sub 4}: 0.2 and 0.4 g/g; {approx}150 times reused) inside the bottom of a batch reactor. Then, a stoichiometric amount of pure liquid water (H{sub 2}O/NaBH{sub 4}: 2-8 mol/mol) was added and the catalyzed NaBH{sub 4} hydrolysis evolved, in the absence of an alkali inhibitor. In this way, this research work is designated alkali free hydrolysis of NaBH{sub 4} for H{sub 2} generation. This type of hydrolysis is excellent from an environmental point of view because it does not involve strongly caustic solutions. Experiments were performed in three batch reactors with internal volumes 646, 369 and 229 cm{sup 3}, and having different bottom geometries (flat and conical shapes). The H{sub 2} generated was a function of the added water and completion was achieved with H{sub 2}O/NaBH{sub 4} = 8 mol/mol. The results show that hydrogen yields and rates increase remarkably increasing both system temperature and pressure. Reactor bottom shape influences deeply H{sub 2} generation: the conical bottom shape greatly enhances the rate and practically eliminates the reaction induction time. Our system of compressed hydrogen generation up to 1.26 MPa shows 6.3 wt% and 70 kg m{sup -3}, respectively, for gravimetric and volumetric hydrogen storage capacities (materials-only basis) and therefore is a viable hydrogen storage candidate for portable applications. (author)

  13. Hydrogen-peroxide epoxidation of natural olefins catalyzed by a dinuclear manganese complex

    NARCIS (Netherlands)

    Mandelli, D; Voitiski, KB; Schuchardt, U; Shul'pin, GB

    2002-01-01

    The complex of Mn(IV) with the macrocyclic N-containing ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (L) [L2Mn2O3](PF6)(2) catalyzes epoxidation of (+)-limonene in CH3CN solution at room temperature. Adding CH3COOH accelerates the reaction. The products are isomers of limonene epoxide with predomi

  14. Short term hydrogen generation following LOCA and loss of ECCS

    International Nuclear Information System (INIS)

    The purpose of the present study is to estimate the amount of hydrogen that can be generated due to metal water reaction following LOCA and loss of ECCS in a 500 MWe PHWR. A computer code HYGEN (Hydrogen Generation) written in FORTRAN calculates time-dependent fuel temperature during the post blowdown period and the amount of hydrogen generated as a result of metal water reaction. It is seen from the analyses that metal water reaction depends on fuel bundle power, its initial temperature and steam flow conditions. At present, four groups of channels have been analysed for different steam flow conditions, and it is found that, for an about 5 gm/sec steam flow condition, the maximum of amount of hydrogen is generated (5.76 x 104 gm-mole) due to the zircaloy - steam reaction. This amount of hydrogen, when considered mixed in volume V1 (drywell) of the reactor building, means that the global concentration reaches about 2.76% by volume. So, it is seen that in the short term, the global hydrogen concentration in the reactor building is well below the flammability limit of 4% by volume. (author) 4 refs., 1 tab., 10 figs

  15. Hydrogen generation via anaerobic fermentation of paper mill wastes.

    Science.gov (United States)

    Valdez-Vazquez, Idania; Sparling, Richard; Risbey, Derek; Rinderknecht-Seijas, Noemi; Poggi-Varaldo, Héctor M

    2005-11-01

    The objective of this work was to determine the hydrogen production from paper mill wastes using microbial consortia of solid substrate anaerobic digesters. Inocula from mesophilic, continuous solid substrate anaerobic digestion (SSAD) reactors were transferred to small lab scale, batch reactors. Milled paper (used as a surrogate paper waste) was added as substrate and acetylene or 2-bromoethanesulfonate (BES) was spiked for methanogenesis inhibition. In the first phase of experiments it was found that acetylene at 1% v/v in the headspace was as effective as BES in inhibiting methanogenic activity. Hydrogen gas accumulated in the headspace of the bottles, reaching a plateau. Similar final hydrogen concentrations were obtained for reactors spiked with acetylene and BES. In the second phase of tests the headspace of the batch reactors was flushed with nitrogen gas after the first plateau of hydrogen was reached, and subsequently incubated, with no further addition of inhibitor nor substrate. It was found that hydrogen production resumed and reached a second plateau, although somewhat lower than the first one. This procedure was repeated a third time and an additional amount of hydrogen was obtained. The plateaux and initial rates of hydrogen accumulation decreased in each subsequent incubation cycle. The total cumulative hydrogen harvested in the three cycles was much higher (approx. double) than in the first cycle alone. We coined this procedure as IV-SSAH (intermittently vented solid substrate anaerobic hydrogen generation). Our results point out to a feasible strategy for obtaining higher hydrogen yields from the fermentation of industrial solid wastes, and a possible combination of waste treatment processes consisting of a first stage IV-SSAH followed by a second SSAD stage. Useful products of this approach would be hydrogen, organic acids or methane, and anaerobic digestates that could be used as soil amenders after post-treatment.

  16. Hydrogen generation via anaerobic fermentation of paper mill wastes

    Energy Technology Data Exchange (ETDEWEB)

    Valdez Vazquez, I.; Poggi Varaldo, H.M. [CINVESTAV-IPN, Mexico D.F. (Mexico). Dept. of Biotechnology and Bioengineering; Sparling, R.; Risbey, D. [Manitoba Univ., Winnipeg (Canada). Dept. of Microbiology; Rinderknecht Seijas, N. [ESIQUIE-IPN, Mexico D.F. (Mexico). Division Base Sciences

    2005-11-15

    The objective of this work was to determine the hydrogen production from paper mill wastes using microbial consortia of solid substrate anaerobic digesters. Inocula from mesophilic, continuous solid substrate anaerobic digestion (SSAD) reactors were transferred to small lab scale, batch reactors. Milled paper (used as a surrogate paper waste) was added as substrate and acetylene or 2-bromoethanesulfonate (BES) was spiked for methanogenesis inhibition. In the first phase of experiments it was found that acetylene at 1% v/v in the headspace was as effective as BES in inhibiting methanogenic activity. Hydrogen gas accumulated in the headspace of the bottles, reaching a plateau. Similar final hydrogen concentrations were obtained for reactors spiked with acetylene and BES. In the second phase of tests the headspace of the batch reactors was flushed with nitrogen gas after the first plateau of hydrogen was reached, and subsequently incubated, with no further addition of inhibitor nor substrate. It was found that hydrogen production resumed and reached a second plateau, although somewhat lower than the first one. This procedure was repeated a third time and an additional amount of hydrogen was obtained. The plateaux and initial rates of hydrogen accumulation decreased in each subsequent incubation cycle. The total cumulative hydrogen harvested in the three cycles was much higher (approx. double) than in the first cycle alone. We coined this procedure as IV-SSAH (intermittently vented solid substrate anaerobic hydrogen generation). Our results point out to a feasible strategy for obtaining higher hydrogen yields from the fermentation of industrial solid wastes, and a possible combination of waste treatment processes consisting of a first stage IV-SSAH followed by a second SSAD stage. Useful products of this approach would be hydrogen, organic acids or methane, and anaerobic digestates that could be used as soil amenders after post-treatment. (author)

  17. Enantioselective Hydrogenation of Aromatic Ketones Catalyzed by Ru Complex Using a New Bipyridyl Diphosphine

    Institute of Scientific and Technical Information of China (English)

    CHEN Li; FU Xing-Li; MING Fang-Yong; CHEN Hua; LI Xian-Jun

    2008-01-01

    A series of RuCl2(bipyridyldiphosphine)(1,2-diamine)complexes were synthesized and applied to the asymmetric hydrogenation of aromatic ketones.Solvent effect and a wide variety of aromatic ketones were explored and up to 96% enantioselectivity was achieved in the hydrogenation of o-bromoacetophenone.

  18. Ruthenium-Catalyzed Transfer Hydrogenation for C-C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs.

    Science.gov (United States)

    Perez, Felix; Oda, Susumu; Geary, Laina M; Krische, Michael J

    2016-06-01

    Merging the chemistry of transfer hydrogenation and carbonyl or imine addition, a broad new family of redox-neutral or reductive hydrohydroxyalkylations and hydroaminomethylations have been developed. In these processes, hydrogen redistribution between alcohols and π-unsaturated reactants is accompanied by C-C bond formation, enabling direct conversion of lower alcohols to higher alcohols. Similarly, hydrogen redistribution between amines to π-unsaturated reactants results in direct conversion of lower amines to higher amines. Alternatively, equivalent products of hydrohydroxyalkylation and hydroaminomethylation may be generated through the reaction of carbonyl compounds or imines with π-unsaturated reactants under the conditions of 2-propanol-mediated reductive coupling. Finally, using vicinally dioxygenated reactants, that is, diol, ketols, or diones, successive transfer hydrogenative coupling occurs to generate 2 C-C bonds, resulting in products of formal [4+2] cycloaddition. PMID:27573275

  19. Oxidative desulfurization of dibenzothiophene with hydrogen peroxide catalyzed by selenium(IV)-containing peroxotungstate.

    Science.gov (United States)

    Hu, Yiwen; He, Qihui; Zhang, Zheng; Ding, Naidong; Hu, Baixing

    2011-11-28

    With stoichiometric H(2)O(2) as oxidant, dibenzothiophene (DBT) is oxidized to its corresponding sulfone with high efficiency, catalyzed by a sub-valence heteronuclear peroxotungstate, [C(18)H(37)N(CH(3))(3)](4)[H(2)Se(IV)(3)W(6)O(34)], under mild biphase conditions and the catalyst shows remarkable selectivity of catalytic oxidation towards DBT, cinnamyl alcohol and quinoline. PMID:21966674

  20. Ruthenium-Catalyzed Selective Hydrogenation of bis-Arylidene Tetramic Acids. Application to the Synthesis of Novel Structurally Diverse Pyrrolidine-2,4-diones

    Directory of Open Access Journals (Sweden)

    Olga Igglessi-Markopoulou

    2011-07-01

    Full Text Available Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data.

  1. Hydrogen Evolution from Water under Aerobic Conditions Catalyzed by a Cobalt ATCUN Metallopeptide.

    Science.gov (United States)

    Kandemir, Banu; Kubie, Lenore; Guo, Yixing; Sheldon, Brian; Bren, Kara L

    2016-02-15

    The cobalt complex of an amino-terminal copper and nickel (ATCUN) motif model tripeptide (CoGGH) is shown to act as an electrocatalyst for hydrogen evolution from water near neutral pH with high Faradaic efficiency. The catalyst performance is not significantly impacted by exposure to oxygen. CoGGH represents a new class of hydrogen evolution catalyst that is straightforward to prepare and to modify.

  2. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Directory of Open Access Journals (Sweden)

    Cláudia M. B. Neves

    2012-01-01

    Full Text Available This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H2O2, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy.

  3. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Neves, Claudia M.B.; Simoes, Mario M.Q.; Domingues, Fernando M.J.; Neves, M. Graca P.M.S.; Cavaleiro, Jose A.S., E-mail: msimoes@ua.pt [Dept. de Quimica, QOPNA, Universidade de Aveiro (Portugal)

    2012-07-01

    This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H{sub 2}O{sub 2}, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy. (author)

  4. Synthesis of Novel Monophosphoramidite Ligands Derived from L-Proline for Rh-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Acid Esters

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Two novel monophosphoramidites were synthesized through a five-step transformation from commercially available L-proline. In the Ph-catalyzed asymmetric hydrogenation of α-dehydroamino acid derivatives, ligand (Sc,Ra)-1b showed good enantioselectivity and up to 91% e.e. was obtained.

  5. Chloride ion-catalyzed generation of difluorocarbene for efficient preparation of gem-difluorinated cyclopropenes and cyclopropanes

    KAUST Repository

    Wang, Fei

    2011-01-01

    A chloride ion-catalyzed generation of difluorocarbene from a relatively non-toxic and inexpensive precursor, Me3SiCF2Cl (1), under mild and neutral conditions leads to an efficient preparation of gem-difluorocyclopropenes and difluorocyclopropanes through [2 + 1] cycloaddition reactions with alkynes and alkenes, respectively. © 2011 The Royal Society of Chemistry.

  6. Generation of correlated photons in hydrogenated amorphous-silicon waveguides

    OpenAIRE

    Clemmen, S.; Perret, A; Selvaraja, Shankar Kumar; Bogaerts, Wim; Van Thourhout, Dries; Baets, Roel; Emplit, Ph.; Massar, S.

    2011-01-01

    We report the first (to our knowledge) observation of correlated photon emission in hydrogenated amorphous- silicon waveguides. We compare this to photon generation in crystalline silicon waveguides with the same geome- try. In particular, we show that amorphous silicon has a higher nonlinearity and competes with crystalline silicon in spite of higher loss.

  7. Supercontinuum generation in hydrogenated amorphous silicon waveguides at telecommunication wavelengths.

    Science.gov (United States)

    Safioui, Jassem; Leo, François; Kuyken, Bart; Gorza, Simon-Pierre; Selvaraja, Shankar Kumar; Baets, Roel; Emplit, Philippe; Roelkens, Gunther; Massar, Serge

    2014-02-10

    We report supercontinuum (SC) generation centered on the telecommunication C-band (1550 nm) in CMOS compatible hydrogenated amorphous silicon waveguides. A broadening of more than 550 nm is obtained in 1cm long waveguides of different widths using as pump picosecond pulses with on chip peak power as low as 4 W.

  8. Hydrogenation of esters catalyzed by ruthenium PN3-Pincer complexes containing an aminophosphine arm

    KAUST Repository

    Chen, Tao

    2014-08-11

    Hydrogenation of esters under mild conditions was achieved using air-stable ruthenium PN3-pincer complexes containing an aminophosphine arm. High efficiency was achieved even in the presence of water. DFT studies suggest a bimolecular proton shuttle mechanism which allows H2 to be activated by the relatively stable catalyst with a reasonably low transition state barrier. © 2014 American Chemical Society.

  9. Hydrogen Peroxide Gas Generator Cycle with a Reciprocating Pump

    Energy Technology Data Exchange (ETDEWEB)

    Whitehead, J C

    2002-06-11

    A four-chamber piston pump is powered by decomposed 85% hydrogen peroxide. The performance envelope of the evolving 400 gram pump has been expanded to 172 cc/s water flow at discharge pressures near 5 MPa. A gas generator cycle system using the pump has been tested under similar conditions of pressure and flow. The powerhead gas is derived from a small fraction of the pumped hydrogen peroxide, and the system starts from tank pressures as low as 0.2 MPa. The effects of steam condensation on performance have been evaluated.

  10. Wind energy-hydrogen storage hybrid power generation

    Energy Technology Data Exchange (ETDEWEB)

    Wenjei Yang; Orhan Aydin [University of Michigan, Ann Arbor, MI (United States). Dept. of Mechanical Engineering and Applied Mechanics

    2001-07-01

    In this theoretical investigation, a hybrid power generation system utilizing wind energy and hydrogen storage is presented. Firstly, the available wind energy is determined, which is followed by evaluating the efficiency of the wind energy conversion system. A revised model of windmill is proposed from which wind power density and electric power output are determined. When the load demand is less than the output of the generation, the excess electric power is relayed to the electrolytic cell where it is used to electrolyse the de-ionized water. Hydrogen thus produced can be stored as hydrogen compressed gas or liquid. Once the hydrogen is stored in an appropriate high-pressure vessel, it can be used in a combustion engine, fuel cell, or burned in a water-cooled burner to produce a very high-quality steam for space heating, or to drive a turbine to generate electric power. It can also be combined with organic materials to produce synthetic fuels. The conclusion is that the system produces no harmful waste and depletes no resources. Note that this system also works well with a solar collector instead of a windmill. (author)

  11. Lactoperoxidase-catalyzed oxidation of thiocyanate by hydrogen peroxide: sup 15 N nuclear magnetic resonance and optical spectral studies

    Energy Technology Data Exchange (ETDEWEB)

    Modi, S.; Deodhar, S.S.; Behere, D.V.; Mitra, S. (Tata Institute of Fundamental Research, Bombay (India))

    1991-01-01

    To establish the agent(s) responsible for the activity of the lactoperoxidase (LPO)/SCN{sup {minus}}/H{sub 2}O{sub 2} system, the oxidation of thiocyanate with hydrogen peroxide, catalyzed by lactoperoxidase, has been studied by {sup 15}N NMR and optical spectroscopy at different concentrations of thiocyanate and hydrogen peroxide and at different pHs. The formation of hypothiocyanite ion (OSCN{sup {minus}}) as one of the oxidation products correlated well with activity of the LPO/SCN{sup {minus}}/H{sub 2}O{sub 2} system and was maximum when the concentrations of the H{sub 2}O{sub 2} and SCN{sup {minus}} were nearly the same and the pH was <6.0. At (H{sub 2}O{sub 2})/(SCN{sup {minus}}) = 1, OSCN{sup {minus}} decomposed very slowly back to thiocyanate. When the ratio (H{sub 2}O{sub 2})/(SCN{sup {minus}}) was above 2, formation of CN{sup {minus}} was observed, which was confirmed by {sup 15}N NMR and also by changes in the optical spectrum of LPO. The oxidation of thiocyanate by H{sub 2}O{sub 2} in the presence of LPO does not take place at pH >8.0. Since thiocyanate does not bind to LPO above this pH, the binding of thiocyanate to LPO is considered to be prerequisite for the oxidation of thiocyanate. Maximum inhibition of oxygen uptake by Streptococcus cremoris 972 bacteria was observed when hydrogen peroxide and thiocyanate were present in equimolar amounts and the pH was below 6.0.

  12. Marrying gas power and hydrogen energy: A catalytic system for combining methane conversion and hydrogen generation

    NARCIS (Netherlands)

    J. Beckers; C. Gaudillère; D. Farrusseng; G. Rothenberg

    2009-01-01

    Ceria-based catalysts are good candidates for integrating methane combustion and hydrogen generation. These new, tuneable catalysts are easily prepared. They are robust inorganic crystalline materials, and perform well at the 400 °C-550 °C range, in some cases even without precious metals. This make

  13. Asymmetric transfer hydrogenation of prochiral ketone catalyzed over Fe-CS/SBA-15 catalyst

    Institute of Scientific and Technical Information of China (English)

    XUE Ping; WU Tao

    2007-01-01

    A heterogeneous chiral catalyst Fe(Ⅲ)-CS (chitosan)complex/mesoporous molecular sieve SBA-15 (Santa Barbara Amorphous) was prepared.The asymmetric transfer hydrogenations of prochiral acetophenone and 4-methyl-2-pentanone to corresponding chiral alcohols were carried out on Fe-CS/SBA-15 at atmosphere pressure using 2-propanol as hydrogen donor.Effects of Fe content in catalyst,reaction temperature,reaction time and promoter KOH concentration on the conversion of substrates and enantioselectivity were investigated.Fe-CS/SBA-15 with 2.2%mass fraction Fe exhibits considerable enantioselectivity and catalytic activity for the asymmetric transfer hydrogenations of aromatic ketone and aliphatic ketone.Under optimal reaction conditions:KOH concentration 0.03 mol/L,reaction temperature 70℃ and reaction time 4 h,enantiomer excess(ee)of (R)-1-phenylethanol and conversion of acetophenone can reach 87.4%and 27.7%,respectively.Under the above KOH concentration and reaction temperature and reaction time of 8 h,the ee of(R)-4-methyl-2-pentanol and conversion 4-methyl-2-pentanone amounted to 50.2%and 25.5%,respectively.

  14. Hydrogen generation from methanolysis of sodium borohydride over Co/Al2O3 catalyst

    Institute of Scientific and Technical Information of China (English)

    Dongyan Xu; Lin Zhao; Ping Dai; Shengfu Ji

    2012-01-01

    Co/Al2O3 catalyst is prepared with an impregnation-chemical reduction method and used to catalyze the methanolysis of sodium borohydride (NaBH4) for hydrogen generation.At solution temperature of 0℃,the methanolysis reaction can be effectively accelerated using Co/Al2O3 catalyst and provide a desirable hydrogen generation rate,which makes it suitable for apphcations under the circumstance of low environmental temperature.The byproduct of methanolysis reaction is analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR).The characterization results indicate that methanol can be easily recovered after methanolysis reaction by hydrolysis of the methanolysis byproduct,NaB(OCH3)4.The catalytic activity of Co/Al2O3 towards NaBH4 methanolysis can be further improved by appropriate calcination treatment.The catalytic methanolysis kinetics and catalyst reusability are also studied over the Co/Al2O3 catalyst calcined at the optimized temperature.

  15. Solar powered hydrogen generating facility and hydrogen powered vehicle fleet. Final technical report, August 11, 1994--January 6, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Provenzano, J.J.

    1997-04-01

    This final report describes activities carried out in support of a demonstration of a hydrogen powered vehicle fleet and construction of a solar powered hydrogen generation system. The hydrogen generation system was permitted for construction, constructed, and permitted for operation. It is not connected to the utility grid, either for electrolytic generation of hydrogen or for compression of the gas. Operation results from ideal and cloudy days are presented. The report also describes the achievement of licensing permits for their hydrogen powered trucks in California, safety assessments of the trucks, performance data, and information on emissions measurements which demonstrate performance better than the Ultra-Low Emission Vehicle levels.

  16. Hydrogenation of Olefins Catalyzed by Polymer-Supported Palladium-Imidazole%聚合物负载的钯-咪唑催化烯烃加氢

    Institute of Scientific and Technical Information of China (English)

    Udayakumar VELU; Alexander STANISLAUS; Gayathri VIRUPAIAH; Shivakumaraiah; Viswanathan BALASUBRAMANIAN

    2011-01-01

    A polymer-supported palladium-imidazole catalyst was used to catalyze the hydrogenation of various olefins under mild conditions. The rate of hydrogenation was studied. The effects of factors such as substrate concentration, catalyst concentration, partial pressure of hydrogen and temperature on initial rate of reaction of selected olefins were investigated. A mechanism for the reaction was proposed from the rate equation. The effects of the solvent and structure of the olefin on the rate of hydrogenation were investigated. The catalyst showed good reusability without any leaching of metal from the support. The homologous analog of the polymer-supported catalyst could not be used as catalyst for the hydrogenation of olefins in methanol because there was precipitation of the metal during reaction.

  17. Generator cooling hydrogen purity improvement system using hydrogen absorbing alloy; Suiso kyuzo gokin riyo hatsudenkinai suiso jundo kojo system

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, H.; Kabutomori, T.; Wakisaka, Y. [Japan Steel Works, Ltd., Tokyo (Japan); Nishimura, Y.; Kogi, T.; Sato, J.; Haruki, N. [Kansai Electric Power Co. Inc., Osaka (Japan); Fujita, T. [Mitsubishi Electric Corp., Tokyo (Japan)

    1998-09-15

    Described herein is a system which uses a hydrogen-absorbing alloy to purify a hydrogen gas stream used as a coolant for power generator. Hydrogen in the stream containing impurities such as nitrogen can be selectively absorbed by sufficiently cooled hydrogen-absorbing alloy. Impurity gases concentrated in the alloy pores are released, and then the alloy is heated to release hydrogen. This purifies hydrogen to at least 99.99%. This system essentially consists of an hydrogen-absorbing unit, hot water production/supply system which circulates hot water of 80 to 90degC to release hydrogen out of the alloy, pretreatment unit, and temperature and pressure sensors. It is confirmed, by the test in which the system is connected to a commercial power generator of 600MW, that the system can be continuously operated to purify hydrogen to at least 99.9% for an extended period. 4 refs., 18 figs., 1 tab.

  18. Generation of hydrogen from photocatalytic cleavage of water

    Energy Technology Data Exchange (ETDEWEB)

    Mallinson, R.G.; Resasco, D.E.; Lobban, L.L.; Nicholas, K.M. [Univ. of Oklahoma, Norman, OK (United States)

    1998-08-01

    This paper describes the objectives, methods and early results on the US Department of Energy sponsored project to generate hydrogen from splitting of water using photocatalysts. The approach uses organometallic photosensitizers adsorbed onto platinated titania. Platinized titania is a photocatalyst for water splitting, but does not absorb sunlight in the visible range, where most of the sun`s energy is contained. Organometallic photosensitizers are synthesized, attached to platinized titania and characterized by UV-Vis spectroscopy, cyclic voltammetry, action spectra and hydrogen generation ability. Thus far, Copper, Iron and Ruthenium catalyst systems have been produced and characterized in this manner. Suitable sensitized systems that have the desirable properties have not yet been found.

  19. Transfer hydrogenation reactions catalyzed by chiral half-sandwich Ruthenium complexes derived from Proline

    Indian Academy of Sciences (India)

    ARUN KUMAR PANDIA KUMAR; ASHOKA G SAMUELSON

    2016-09-01

    Chiral ruthenium half-sandwich complexes were prepared using a chelating diamine made from proline with a phenyl, ethyl, or benzyl group, instead of hydrogen on one of the coordinating arms. Three of these complexes were obtained as single diastereoisomers and their configuration identified by X-ray crystallography. The complexes are recyclable catalysts for the reduction of ketones to chiral alcohols in water. A ruthenium hydride species is identified as the active species by NMR spectroscopy and isotopic labelling experiments.Maximum enantio-selectivity was attained when a phenyl group was directly attached to the primary amine on the diamine ligand derived from proline.

  20. Asymmetric transfer hydrogenation of ketones catalyzed by nickel complex with new PNO-type ligands

    Institute of Scientific and Technical Information of China (English)

    Zhen Rong Dong; Yan Yun Li; Shen Luan Yu; Guo Song Sun; Jing Xing Gao

    2012-01-01

    The new polydentate mixed-N,P,O chiral ligands have been synthesized by the condensation of bis(o-formylphenyl)-phenylphosphane and R-phenylglycinol in CHCl3,and fully characterized by IR,NMR and EIMS spectra.These ligands were employed with a simple Ni complex Ni(PPh8)2Cl2 in situ as catalytic systems for asymmetric transfer hydrogenation of ketones,and the corresponding optical alcohols were obtained with up to 84% ee under mild conditions.

  1. Hydrogen generation during molten-fuel-coolant interactions

    International Nuclear Information System (INIS)

    Given the absence of adequate cooling water to the core of a light-water reactor, the fission product decay heat would eventually cause the reactor fuel and cladding to melt. This could lead to slumping of the molten core materials into the lower plenum of the reactor vessel, possibly followed by failure of the vessel wall and pouring of the molten materials into the reactor cavity. Recent analyses have indicated that residual water is likely to be present both in the lower plenum and in the reactor cavity. Therefore, when the molten core materials enter either region, there is a strong probability of molten core contacting water. The physical process by which the molten core contacts and mixes with the water is important for two reasons: (1) because of its potential for rapid steam generation from a fuel-coolant interaction (FCI) either energetic or non-energetic; and (2) because it is a source of combustible hydrogen from the oxidation of the metallic components of the molten core. In this paper the rate of hydrogen generation due to fuel-coolant mixing is the major topic. To predict this one must understand two physical processes. The first is the degree of fuel breakup during the mixing phase and during the FCI. By understanding this process one is able to calculate the surface area available during the chemical reaction. The second is the rate of hydrogen generation per unit area when the fuel is molten and as it cools and solidifies

  2. DWPF Hydrogen Generation Study-Form of Noble Metal SRAT Testing

    Energy Technology Data Exchange (ETDEWEB)

    Bannochie, C

    2005-09-01

    The Defense Waste Processing Facility, DWPF, has requested that the Savannah River National Laboratory, SRNL, investigate the factors that contribute to hydrogen generation to determine if current conservatism in setting the DWPF processing window can be reduced. A phased program has been undertaken to increase understanding of the factors that influence hydrogen generation in the DWPF Chemical Process Cell, CPC. The hydrogen generation in the CPC is primarily due to noble metal catalyzed decomposition of formic acid with a minor contribution from radiolytic processes. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Two sludge simulants were obtained, one with co-precipitated noble metals and one without noble metals. Co-precipitated noble metals were expected to better match real waste behavior than using trimmed noble metals during CPC simulations. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The two original and two heat-treated sludge simulants were then used as feeds to Sludge Receipt and Adjustment Tank, SRAT, process simulations. Testing was done at relatively high acid stoichiometries, {approx}175%, and without mercury in order to ensure significant hydrogen generation. Hydrogen generation rates were monitored during processing to assess the impact of the form of noble metals. The following observations were made on the data: (1) Co-precipitated noble metal simulant processed similarly to trimmed noble metal simulant in most respects, such as nitrite to nitrate conversion, formate destruction, and pH, but differently with respect to hydrogen generation: (A

  3. Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters.

    Science.gov (United States)

    Li, Yuehui; Topf, Christoph; Cui, Xinjiang; Junge, Kathrin; Beller, Matthias

    2015-04-20

    Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. PMID:25728921

  4. Silver-catalyzed silicon-hydrogen bond functionalization by carbene insertion.

    Science.gov (United States)

    Iglesias, M José; Nicasio, M Carmen; Caballero, Ana; Pérez, Pedro J

    2013-01-28

    The catalytic functionalization of silicon-hydrogen bonds by means of the insertion of carbene units :CHCO(2)Et from ethyl diazoacetate (EDA) has been achieved using a silver-based catalyst, constituting the first example of this metal to promote this transformation. Competition experiments have revealed that the relative reactivity of substituted silanes depends on the bond dissociation energy of the Si-H bond (tertiary > secondary > primary for ethyl substituted). In the presence of bulky substituents such order reverts to secondary > primary ≈ tertiary (for phenyl substituted). Screening with other diazo compounds has shown that N(2)C(Ph)CO(2)Et displays similar reactivity to that of EDA, whereas other N(2)C(R)CO(2)Et (R = Me, CO(2)Et) gave lower conversions. PMID:23114570

  5. Polystyrene-supported triphenylarsines: Useful ligands in palladium-catalyzed aryl halide homocoupling reactions and a catalyst for alkene epoxidation using hydrogen peroxide

    OpenAIRE

    Song He, H; Zhang, C; Ng, CKW; Toy, PH

    2005-01-01

    The utility of both soluble (non-cross-linked) and insoluble (cross-linked) polystyrene-supported triphenylarsine reagents were examined. These reagents were prepared by standard radical polymerization methodology and used in palladium-catalyzed homocoupling reactions of aryl halides. The insoluble reagent was also used as a catalyst precursor in heterogeneous alkene epoxidation reactions in which aqueous hydrogen peroxide was the stoichiometric oxidant. For the aryl halide homocoupling react...

  6. Selective Oxidation of Toluene with Hydrogen Peroxide Catalyzed by V-Mo-based Catalyst

    Institute of Scientific and Technical Information of China (English)

    WU Jun-ping; WANG Xue-qin; ZHU Liang-fang; LI Gui-ying; HU Chang-wei

    2007-01-01

    The selective catalytic oxidation of toluene with hydrogen peroxide over V-Mo-based catalysts under mild conditions was studied. The promotion effect of Mo on the catalysts was studied with V/Al2O3 and Mo/Al2O3 as reference samples. The catalysts were characterized by XRD, TPR, and XPS techniques. The results show that the addition of Mo to V/Al2O3 may change the distribution of V species on Al2O3 surface. Over V-Mo/Al2O3 catalyst, highly dispersed amorphous V species facilitates benzaldehyde formation, and crystalline V2O5 species increases the conversion of toluene but decreases the selectivity to benzaldehyde, while AlVMoO7 species favors both the conversion of toluene and the formation of cresols. The yield of benzaldehyde depends remarkably on the surface O/Al and Mo/V atomic ratios, and gets to a maximum value of 13.2% with a selectivity of 79.5% at an O/Al atomic ratio of 3.0 and Mo/V atomic ratio of 0.7.

  7. Sum Frequency Generation Studies of Hydrogenation Reactions on Platinum Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Krier, James M. [Univ. of California, Berkeley, CA (United States)

    2013-08-31

    Sum Frequency Generation (SFG) vibrational spectroscopy is used to characterize intermediate species of hydrogenation reactions on the surface of platinum nanoparticle catalysts. In contrast to other spectroscopy techniques which operate in ultra-high vacuum or probe surface species after reaction, SFG collects information under normal conditions as the reaction is taking place. Several systems have been studied previously using SFG on single crystals, notably alkene hydrogenation on Pt(111). In this thesis, many aspects of SFG experiments on colloidal nanoparticles are explored for the first time. To address spectral interference by the capping agent (PVP), three procedures are proposed: UV cleaning, H2 induced disordering and calcination (core-shell nanoparticles). UV cleaning and calcination physically destroy organic capping while disordering reduces SFG signal through a reversible structural change by PVP.

  8. A New Method for Generating Hydrogen from Water

    Institute of Scientific and Technical Information of China (English)

    MENG Qing-Bo; LI Ke-Xin; LI Hong; FAN Yu-Zun; YU Zhe-Xun; LI Dong-Mei; LUO Yan-Hong; CHEN Li-Quan

    2008-01-01

    A new method for generating hydrogen by the reaction of A1 powder with water using iodine as additive is developed. 12 can penetrate through the surface oxide layer on atuminium to form AlI3. High solubility of AlI3 in water is benefited to activate Al surface. It is found that the production of hydrogen becomes significant above 60℃ and obeys a logarithm rule. The pH value varies from 5 to 3 then back to 4.5 during the reaction,which is determined mainly by the kinetics of hydration reaction of AlI3 and the reaction of Al and HI produced spontaneously.

  9. Nitric-glycolic flowsheet testing for maximum hydrogen generation rate

    Energy Technology Data Exchange (ETDEWEB)

    Martino, C. J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Newell, J. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Williams, M. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-03-01

    The Defense Waste Processing Facility (DWPF) at the Savannah River Site is developing for implementation a flowsheet with a new reductant to replace formic acid. Glycolic acid has been tested over the past several years and found to effectively replace the function of formic acid in the DWPF chemical process. The nitric-glycolic flowsheet reduces mercury, significantly lowers the chemical generation of hydrogen and ammonia, allows purge reduction in the Sludge Receipt and Adjustment Tank (SRAT), stabilizes the pH and chemistry in the SRAT and the Slurry Mix Evaporator (SME), allows for effective adjustment of the SRAT/SME rheology, and is favorable with respect to melter flammability. The objective of this work was to perform DWPF Chemical Process Cell (CPC) testing at conditions that would bound the catalytic hydrogen production for the nitric-glycolic flowsheet.

  10. Hydrogen Generation from Photocatalytic Silver|Zinc Oxide Nanowires: Towards Multifunctional Multisegmented Nanowire Devices

    NARCIS (Netherlands)

    Maijenburg, A. Wouter; Rodijk, Eddy J.B.; Maas, Michiel G.; Enculescu, Monica; Blank, Dave H.A.; Elshof, ten Johan E.

    2011-01-01

    Photoactive nanowires: A novel photo-electrochemical nanowire diode that catalyzes the conversion of methanol and water to hydrogen under UV light is demonstrated. The wire consists of a metal and a metal oxide segment that are connected via a Schottky barrier. Other functions, such as remote- contr

  11. Hydrogenation of phenylpyruvic acid to phenylalanine catalyzed by Ni-B/SiO2

    Institute of Scientific and Technical Information of China (English)

    Qunfang Liang; Aiqing Zhang; Lin Li

    2008-01-01

    Phenylalanine(Phe)is a significant amino acid that cannot be synthesized by human themselves but must be taken from environment.It was initially found that the nanosized amorphous Ni-B/SiO2 alloy prepared by the chemical reduction method was an effective catalyst for the preparation of Phe from phenylpyruvic acid(PPA)by amination and hydrogenation.It has been found that the amorphous Ni-B/SiO2 alloy catalyst exhibits superior activity and selectivity to the traditional catalysts Raney Nj and Urushibara nickel.The effects of reaction time.amounts of catalysts and ammonia solution,reaction temperature,and H2 pressure on the reaction have been investigated systematically.The results indicated that the yield of Phe was 97.9%.and the selectivity for Phe reached 98.9%when the reaction was carried out for 3 h at 333 K and 2.0 Mpa of H2 with m(Cat.):m(PPA)=0.6:1.0 and n(NH3):n(PPA)=3:1.The catalysts were characterized by XRD,AAS,XPS,BET,and TEM.and the relationship between the catalyst structure and the catalytic activity was discussed in detail.It was found that the reason why Ni-B/SiO2 amorphous alloy catalyst was much more active for the preparation of Phe could be accounted for by the presence of electron-rich Ni due to electron donation from alloying B:the smaller size of Ni-B particles,the larger specific surface area of Ni-B/SiO2.

  12. Atomistic Modelling of Materials for Clean Energy Applications : hydrogen generation, hydrogen storage, and Li-ion battery

    OpenAIRE

    Qian, Zhao

    2013-01-01

    In this thesis, a number of clean-energy materials for hydrogen generation, hydrogen storage, and Li-ion battery energy storage applications have been investigated through state-of-the-art density functional theory. As an alternative fuel, hydrogen has been regarded as one of the promising clean energies with the advantage of abundance (generated through water splitting) and pollution-free emission if used in fuel cell systems. However, some key problems such as finding efficient ways to prod...

  13. A water soluble electro-catalyst for generating hydrogen based on a cobalt(III) complex supported by 1,10-phenanthroline

    Science.gov (United States)

    Peng, Qiu-Xia; Tang, Ling-Zhi; Ren, Shi-Tao; Ye, Li-Ping; Deng, Yuan-Fu; Zhan, Shu-Zhong

    2016-10-01

    As we know, coordinatively unsaturated complexes can catalyze hydrogen generation via an unstable hydride intermediate. In this paper, we report an electrocatalyst based on a water soluble coordinatively saturated complex, [(phen)2Co(CN)2]·NO31 that is formed by the reaction of 1,10-phenanthroline (phen), Co(NO3)2·6H2O and tetracyanoethylene (TCNE). Its structure has been characterized by physics-chemical and spectroscopic methods. Complex 1 can electrocatalyze hydrogen evolution both from acetic acid and aqueous buffer.

  14. Converting Chemical Energy to Electricity through a Three-Jaw Mini-Generator Driven by the Decomposition of Hydrogen Peroxide.

    Science.gov (United States)

    Xiao, Meng; Wang, Lei; Ji, Fanqin; Shi, Feng

    2016-05-11

    Energy conversion from a mechanical form to electricity is one of the most important research advancements to come from the horizontal locomotion of small objects. Until now, the Marangoni effect has been the only propulsion method to produce the horizontal locomotion to induce an electromotive force, which is limited to a short duration because of the specific property of surfactants. To solve this issue, in this article we utilized the decomposition of hydrogen peroxide to provide the propulsion for a sustainable energy conversion from a mechanical form to electricity. We fabricated a mini-generator consisting of three parts: a superhydrophobic rotator with three jaws, three motors to produce a jet of oxygen bubbles to propel the rotation of the rotator, and three magnets integrated into the upper surface of the rotator to produce the magnet flux. Once the mini-generator was placed on the solution surface, the motor catalyzed the decomposition of hydrogen peroxide. This generated a large amount of oxygen bubbles that caused the generator and integrated magnets to rotate at the air/water interface. Thus, the magnets passed under the coil area and induced a change in the magnet flux, thus generating electromotive forces. We also investigated experimental factors, that is, the concentration of hydrogen peroxide and the turns of the solenoid coil, and found that the mini-generator gave the highest output in a hydrogen peroxide solution with a concentration of 10 wt % and under a coil with 9000 turns. Through combining the stable superhydrophobicity and catalyst, we realized electricity generation for a long duration, which could last for 26 000 s after adding H2O2 only once. We believe this work provides a simple process for the development of horizontal motion and provides a new path for energy reutilization. PMID:27093949

  15. GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II DECHEMA; GREEN SOLVENTS FOR CATALYSIS - ENVIRONMENTALLY BENIGN REACTION MEDIA

    Science.gov (United States)

    Green catalyzed oxidation of hydrocarbons in alternative solvent systems generated by PARIS IIThomas M. Becker, Michael A. Gonzalez, Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Mar...

  16. HYDROGEN GENERATION FROM ELECTROLYSIS - REVISED FINAL TECHNICAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    IBRAHIM, SAMIR; STICHTER, MICHAEL

    2008-07-31

    DOE GO13028-0001 DESCRIPTION/ABSTRACT This report is a summary of the work performed by Teledyne Energy Systems to understand high pressure electrolysis mechanisms, investigate and address safety concerns related to high pressure electrolysis, develop methods to test components and systems of a high pressure electrolyzer, and produce design specifications for a low cost high pressure electrolysis system using lessons learned throughout the project. Included in this report are data on separator materials, electrode materials, structural cell design, and dissolved gas tests. Also included are the results of trade studies for active area, component design analysis, high pressure hydrogen/oxygen reactions, and control systems design. Several key pieces of a high pressure electrolysis system were investigated in this project and the results will be useful in further attempts at high pressure and/or low cost hydrogen generator projects. An important portion of the testing and research performed in this study are the safety issues that are present in a high pressure electrolyzer system and that they can not easily be simplified to a level where units can be manufactured at the cost goals specified, or operated by other than trained personnel in a well safeguarded environment. The two key objectives of the program were to develop a system to supply hydrogen at a rate of at least 10,000 scf/day at a pressure of 5000psi, and to meet cost goals of $600/ kW in production quantities of 10,000/year. On these two points TESI was not successful. The project was halted due to concerns over safety of high pressure gas electrolysis and the associated costs of a system which reduced the safety concerns.

  17. Broad Spectrum Photoelectrochemical Diodes for Solar Hydrogen Generation

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Craig A.

    2014-11-26

    Under program auspices we have investigated material chemistries suitable for the solar generation of hydrogen by water photoelectrolysis. We have built upon, and extended, our knowledge base on the synthesis and application of TiO2 nanotube arrays, a material architecture that appears ideal for water photoelectrolysis. To date we have optimized, refined, and greatly extended synthesis techniques suitable for achieving highly ordered TiO2 nanotube arrays of given length, wall thickness, pore diameter, and tube-to-tube spacing for use in water photoelectrolysis. We have built upon this knowledge based to achieve visible light responsive, photocorrosion stable n-type and p-type ternary oxide nanotube arrays for use in photoelectrochemical diodes.

  18. Photocatalytic Hydrogen Generation by CdSe/CdS Nanoparticles.

    Science.gov (United States)

    Qiu, Fen; Han, Zhiji; Peterson, Jeffrey J; Odoi, Michael Y; Sowers, Kelly L; Krauss, Todd D

    2016-09-14

    The photocatalytic hydrogen (H2) production activity of various CdSe semiconductor nanoparticles was compared including CdSe and CdSe/CdS quantum dots (QDs), CdSe quantum rods (QRs), and CdSe/CdS dot-in-rods (DIRs). With equivalent photons absorbed, the H2 generation activity orders as CdSe QDs ≫ CdSe QRs > CdSe/CdS QDs > CdSe/CdS DIRs, which is surprisingly the opposite of the electron-hole separation efficiency. Calculations of photoexcited surface charge densities are positively correlated with the H2 production rate and suggest the size of the nanoparticle plays a critical role in determining the relative efficiency of H2 production. PMID:27478995

  19. Nitrogen-Doped Graphene for Photocatalytic Hydrogen Generation.

    Science.gov (United States)

    Chang, Dong Wook; Baek, Jong-Beom

    2016-04-20

    Photocatalytic hydrogen (H2 ) generation in a water splitting process has recently attracted tremendous interest because it allows the direct conversion of clean and unlimited solar energy into the ideal energy resource of H2 . For efficient photocatalytic H2 generation, the role of the photocatalyst is critical. With increasing demand for more efficient, sustainable, and cost-effective photocatalysts, various types of semiconductor photocatalysts have been intensively developed. In particular, on the basis of its superior catalytic and tunable electronic properties, nitrogen-doped graphene is a potential candidate for a high-performance photocatalyst. Nitrogen-doped graphene also offers additional advantages originating from its unique two-dimensional sp(2) -hybridized carbon network including a large specific surface area and exceptional charge transport properties. It has been reported that nitrogen-doped graphene can play diverse but positive functions including photo-induced charge acceptor/meditator, light absorber from UV to visible light, n-type semiconductor, and giant molecular photocatalyst. Herein, we summarize the recent progress and general aspects of nitrogen-doped graphene as a photocatalyst for photocatalytic H2 generation. In addition, challenges and future perspectives in this field are also discussed. PMID:26762892

  20. Development of a new hydrogen purification system by using hydrogen absorbing alloy for generator cooling; Suiso kyuzo gokin riyo hatsudenkinai suiso jundo kojo system no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Haruki, N.; Sato, J.; Kogi, T.; Nishimura, Y. [Kansai Electric Power Co., Inc., Osaka (Japan); Takeda, H. [Japan Steel works Ltd., Tokyo (Japan)] Fujita, T. [Mitsubishi Electric Corp., Tokyo (Japan)

    1997-05-20

    Hydrogen absorbing alloys have a number of useful functions, such as energy conversion, hydrogen storage and purification. As an application to separation and purification of hydrogen, we have developed a new hydrogen purification system by using a hydrogen absorbing alloy for generator cooling. For demonstration testing with an actual machine, a hydrogen recovery and purification device using 120kg of alloy was manufactured and installed on No.5 turbine-synchronous generator at Himeji No.2 power station. This device is designed to improve the purity of the hydrogen gas in generator containing impurities such as nitrogen and oxygen. The test results tell that the purity of the hydrogen gas in the generator can be enhanced from 98% to 99.9% and maintained at this level under continuous operation. An application of the hydrogen purification system is expected to decrease the generator`s windage loss, resulting higher generator efficiency. 2 refs., 18 figs.

  1. Spark Discharge Generated Nanoparticles for Hydrogen Storage Applications

    NARCIS (Netherlands)

    Vons, V.A.

    2010-01-01

    One of the largest obstacles to the large scale application of hydrogen powered fuel cell vehicles is the absence of hydrogen storage methods suitable for application on-board of these vehicles. Metal hydrides are materials in which hydrogen is reversibly absorbed by one or more metals or combinatio

  2. Generation mechanism of hydrogen gas from hardened cement paste by γ-irradiation

    International Nuclear Information System (INIS)

    Hydrogen gas is generated from cementitious waste forms by radiolysis of water. In the case of low level radioactive waste, gas yields have been confirmed to be sufficiently low by irradiation experiments. However, studies have suggested that the hydrogen generation rate in cementitious waste forms is larger than the rate calculated form the g-value (H2 yields for 100eV absorbed). In this paper, the factors that increase the gas generation were investigated quantitatively. Two factors were identified, the effect of an organic diethylene glycol which reacts with hydrogen radicals to produce hydrogen, and the effect of electrons generated in the cementitious matrix which decompose water to hydrogen. The hydrogen generation rate was confirmed to drop less than the rate calculated from the g-value when these factors were eliminated

  3. Justification procedure of hydrogen safety of RU BN compartments as exemplified by steam generator box

    International Nuclear Information System (INIS)

    Basic proposals on completing calculational procedures of sodium cooled reactors hydrogen safety justification, particularly steam generator (SG) box, are presented. It is pointed out that hydrogen appearance in SG box is possible only in accidents with multiple failures. The data presented shows that hydrogen safety and explosion-proofness of fast reactor facility SG box are provided without any special complex and expensive means

  4. Transfer Hydrogenation of C= C Double Bonds Catalyzed by Ruthenium Amido-Complexes:Scopes, Limitation and Enantioselectivity

    Institute of Scientific and Technical Information of China (English)

    XUE,Dong; CHENG,Ying-Chun; CUI,Xin; WANG,Qi-Wei; ZHU,Jin; DENG,Jin-Gen

    2004-01-01

    @@ The reduction of C = C double bonds is one of the most fundamental synthetic transformations and plays a key role in the manufacturing of a wide variety of bulk and fine chemicals. Hydrogenation of olefinic substrates can be achieved readily with molecular hydrogen in many cases, but transfer hydrogenation methods using suitable donor molecules such as formic acid or alcohols are receiving increasing attention as possible synthetic alternatives because it requires no special equipment and avoids the handling of potentially hazardous gaseous hydrogen.

  5. In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts.

    Science.gov (United States)

    Zieliński, Grzegorz Krzysztof; Samojłowicz, Cezary; Wdowik, Tomasz; Grela, Karol

    2015-03-01

    A system for transfer hydrogenation of alkenes, composed of a ruthenium metathesis catalyst and HCOOH, is presented. This operationally simple system can be formed directly after a metathesis reaction to effect hydrogenation of the metathesis product in a single-pot. These hydrogenation conditions are applicable to a wide range of alkenes and offer remarkable selectivity.

  6. In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts.

    Science.gov (United States)

    Zieliński, Grzegorz Krzysztof; Samojłowicz, Cezary; Wdowik, Tomasz; Grela, Karol

    2015-03-01

    A system for transfer hydrogenation of alkenes, composed of a ruthenium metathesis catalyst and HCOOH, is presented. This operationally simple system can be formed directly after a metathesis reaction to effect hydrogenation of the metathesis product in a single-pot. These hydrogenation conditions are applicable to a wide range of alkenes and offer remarkable selectivity. PMID:25586518

  7. Stereo-specificity for pro-(R) hydrogen of NAD(P)H during enzyme-catalyzed hydride transfer to CL-20.

    Science.gov (United States)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2005-12-01

    A dehydrogenase from Clostridium sp. EDB2 and a diaphorase from Clostridium kluyveri were reacted with CL-20 to gain insights into the enzyme-catalyzed hydride transfer to CL-20, and the enzyme's stereo-specificity for either pro-R or pro-S hydrogens of NAD(P)H. Both enzymes biotransformed CL-20 at rates of 18.5 and 24nmol/h/mg protein, using NADH and NADPH as hydride-source, respectively, to produce a N-denitrohydrogenated product with a molecular weight of 393Da. In enzyme kinetics studies using reduced deuterated pyridine nucleotides, we found a kinetic deuterium isotopic effect of 2-fold on CL-20 biotransformation rate using dehydrogenase enzyme against (R)NADD as a hydride-source compared to either (S)NADD or NADH. Whereas, in case of diaphorase, the kinetic deuterium isotopic effect of about 1.5-fold was observed on CL-20 biotransformation rate using (R)NADPD as hydride-source. In a comparative study with LC-MS, using deuterated and non-deuterated NAD(P)H, we found a positive mass-shift of 1Da in the N-denitrohydrogenated product suggesting the involvement of a deuteride (D(-)) transfer from NAD(P)D. The present study thus revealed that both dehydrogenase and diaphorase enzymes from the two Clostridium species catalyzed a hydride transfer to CL-20 and showed stereo-specificity for pro-R hydrogen of NAD(P)H. PMID:16225844

  8. Dependable Hydrogen and Industrial Heat Generation from the Next Generation Nuclear Plant

    Energy Technology Data Exchange (ETDEWEB)

    Charles V. Park; Michael W. Patterson; Vincent C. Maio; Piyush Sabharwall

    2009-03-01

    The Department of Energy is working with industry to develop a next generation, high-temperature gas-cooled nuclear reactor (HTGR) as a part of the effort to supply the US with abundant, clean and secure energy. The Next Generation Nuclear Plant (NGNP) project, led by the Idaho National Laboratory, will demonstrate the ability of the HTGR to generate hydrogen, electricity, and high-quality process heat for a wide range of industrial applications. Substituting HTGR power for traditional fossil fuel resources reduces the cost and supply vulnerability of natural gas and oil, and reduces or eliminates greenhouse gas emissions. As authorized by the Energy Policy Act of 2005, industry leaders are developing designs for the construction of a commercial prototype producing up to 600 MWt of power by 2021. This paper describes a variety of critical applications that are appropriate for the HTGR with an emphasis placed on applications requiring a clean and reliable source of hydrogen. An overview of the NGNP project status and its significant technology development efforts are also presented.

  9. Manganese(II) catalyzes the bicarbonate-dependent oxidation of amino acids by hydrogen peroxide and the amino acid-facilitated dismutation of hydrogen peroxide.

    OpenAIRE

    Berlett, B S; Chock, P B; Yim, M B; Stadtman, E. R.

    1990-01-01

    In bicarbonate/CO2 buffer, Mn(II) and Fe(II) catalyze the oxidation of amino acids by H2O2 and the dismutation of H2O2. As the Mn(II)/Fe(II) ratio is increased, the yield of carbonyl compounds per mole of leucine oxidized is essentially constant, but the ratio of alpha-ketoisocaproate to isovaleraldehyde formed increases, and the fraction of H2O2 converted to O2 increases. In the absence of Fe(II), the rate of Mn(II)-catalyzed leucine oxidation is directly proportional to the H2O2, Mn(II), an...

  10. Hydrogen Plasma Generation with 200 MHz RF Ion Source

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jeongtae; Park, Kwangmook; Seo, Dong Hyuk; Kim, Han-Sung; Kwon, Hyeok-Jung; Cho, Yong-Sub [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-10-15

    The ion source for the system is required to be rugged with 2000 hours maintenance free operation time because it is installed in the vessel filled with SF6 gas at the pressure of 10 bar. A 200 MHz RF ion source is considered as an ion source. It is a simple construction and provides long life operation. The specifications of the ion source are 5 kV extraction voltage and 1 mA beam current referenced to the proton. RF ion source has been developed and undergone a performance test. Results of the test are presented. 200 MHz RF ion source is designated and manufactured. First of all test stand test of ion source are set up for a performance test of ion source. It includes a RF ion source, a 200-MHz RF system, beam extraction system, vacuum system, beam extraction system, and beam diagnostic system. At pressure of 1.2E-5 torr, hydrogen plasma is generated with net RF power 70 W. Pyrex tube surrounded by an inductive coil takes the role of vessel and discharge is enhanced with field of permanent magnets.

  11. Integrated photoelectrochemical energy storage: solar hydrogen generation and supercapacitor.

    Science.gov (United States)

    Xia, Xinhui; Luo, Jingshan; Zeng, Zhiyuan; Guan, Cao; Zhang, Yongqi; Tu, Jiangping; Zhang, Hua; Fan, Hong Jin

    2012-01-01

    Current solar energy harvest and storage are so far realized by independent technologies (such as solar cell and batteries), by which only a fraction of solar energy is utilized. It is highly desirable to improve the utilization efficiency of solar energy. Here, we construct an integrated photoelectrochemical device with simultaneous supercapacitor and hydrogen evolution functions based on TiO(2)/transition metal hydroxides/oxides core/shell nanorod arrays. The feasibility of solar-driven pseudocapacitance is clearly demonstrated, and the charge/discharge is indicated by reversible color changes (photochromism). In such an integrated device, the photogenerated electrons are utilized for H(2) generation and holes for pseudocapacitive charging, so that both the reductive and oxidative energies are captured and converted. Specific capacitances of 482 F g(-1) at 0.5 A g(-1) and 287 F g(-1) at 1 A g(-1) are obtained with TiO(2)/Ni(OH)(2) nanorod arrays. This study provides a new research strategy for integrated pseudocapacitor and solar energy application.

  12. Ruthenium-Catalyzed Asymmetric Hydrohydroxyalkylation of Butadiene: The Role of the Formyl Hydrogen Bond in Stereochemical Control

    Science.gov (United States)

    Grayson, Matthew N.; Krische, Michael J.; Houk, K. N.

    2016-01-01

    The catalyst generated in situ from RuH2(CO)(PPh3)3, (S)-SEGPHOS, and a chiral phosphoric acid promotes asymmetric hydrohydroxyalkylation of butadiene and affords enantioenriched α-methyl homoallylic alcohols. The observed diastereo- and enantioselectivities are determined by both the chiral phosphine and chiral phosphate ligands. Density functional theory calculations (M06/SDD-6-311G(d,p)-IEFPCM(acetone)//B3LYP/SDD-6-31G(d)) predict that the product distribution is controlled by the kinetics of carbon-carbon bond formation, and this process occurs via a closed-chair Zimmerman-Traxler-type transition structure (TS). Chiral phosphate-dependent stereoselectivity arising from this TS is enabled through a hydrogen bond between the phosphoryl oxygen and the aldehyde formyl proton present in TADDOL-derived catalysts. This interaction is absent in the corresponding BINOL-derived systems and the opposite sense of attack on the aldehyde occurs. Additional factors influencing stereochemical control are determined. PMID:26107070

  13. Effective hydrogen generation and resource circulation based on sulfur cycle system

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Hideyuki; Mabuchi, Takashi; Hayashi, Tsugumi; Yokoyama, Shun; Tohji, Kazuyuki [Graduate School of Environmental Studies, Tohoku University 6-6-20, Aramaki, Aoba-ku, Sendai, 980-8579 (Japan)

    2013-12-10

    For the effective hydrogen generation from H{sub 2}S, it should be compatible that the increscent of the photocatalytic (or electrochemical) activities and the development of effective utilization method of by-products (poly sulfide ion). In this study, “system integration” to construct the sulfur cycle system, which is compatible with the increscent of the hydrogen and or electron energy generation ratio and resource circulation, is investigated. Photocatalytic hydrogen generation rate can be enhanced by using stratified photocatalysts. Photo excited electron can be transpired to electrode to convert the electron energy to hydrogen energy. Poly sulfide ion as the by-products can be transferred into elemental sulfur and/or industrial materials such as rubber. Moreover, elemental sulfur can be transferred into H{sub 2}S which is the original materials for hydrogen generation. By using this “system integration”, the sulfur cycle system for the new energy generation can be constructed.

  14. Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS2 layers

    International Nuclear Information System (INIS)

    Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS2, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS2 layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS2 film resulted in hydrogen evolution. Our work shows that 2D MoS2 is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS2 shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS2 is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer

  15. Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS2 layers

    Directory of Open Access Journals (Sweden)

    R. K. Joshi

    2016-01-01

    Full Text Available Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D MoS2, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS2 layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS2 film resulted in hydrogen evolution. Our work shows that 2D MoS2 is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS2 shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS2 is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.

  16. Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, R. K., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in; Sahajwalla, V. [Centre for Sustainable Materials Research and Technology, School of Materials Science and Engineering, University of New South Wales, NSW 2052 (Australia); Shukla, S.; Saxena, S. [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai (India); Lee, G.-H. [Department of Material Science and Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of); Alwarappan, S., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in [CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India)

    2016-01-15

    Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows that 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.

  17. Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS2 layers

    Science.gov (United States)

    Joshi, R. K.; Shukla, S.; Saxena, S.; Lee, G.-H.; Sahajwalla, V.; Alwarappan, S.

    2016-01-01

    Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS2, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS2 layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS2 film resulted in hydrogen evolution. Our work shows that 2D MoS2 is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS2 shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS2 is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.

  18. Atmospheric Hydrogenation of Esters Catalyzed by PNP-Ruthenium Complexes with an N-Heterocyclic Carbene Ligand.

    Science.gov (United States)

    Ogata, Osamu; Nakayama, Yuji; Nara, Hideki; Fujiwhara, Mitsuhiko; Kayaki, Yoshihito

    2016-08-01

    New pincer ruthenium complexes bearing a monodentate N-heterocyclic carbene ligand were synthesized and demonstrated as powerful hydrogenation catalysts. With an atmospheric pressure of hydrogen gas, aromatic, heteroaromatic, and aliphatic esters as well as lactones were converted into the corresponding alcohols at 50 °C. This reaction protocol offers reliable access to alcohols using an easy operational setup. PMID:27439106

  19. Atmospheric Hydrogenation of Esters Catalyzed by PNP-Ruthenium Complexes with an N-Heterocyclic Carbene Ligand.

    Science.gov (United States)

    Ogata, Osamu; Nakayama, Yuji; Nara, Hideki; Fujiwhara, Mitsuhiko; Kayaki, Yoshihito

    2016-08-01

    New pincer ruthenium complexes bearing a monodentate N-heterocyclic carbene ligand were synthesized and demonstrated as powerful hydrogenation catalysts. With an atmospheric pressure of hydrogen gas, aromatic, heteroaromatic, and aliphatic esters as well as lactones were converted into the corresponding alcohols at 50 °C. This reaction protocol offers reliable access to alcohols using an easy operational setup.

  20. Method of generating hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S; Niemann, Michael U; Goswami, D. Yogi; Stefanakos, Elias K

    2013-05-14

    A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

  1. Empirical rate equation model of hydrogen generation for Hanford tank waste

    International Nuclear Information System (INIS)

    Hydrogen is the major flammable gas produced from radioactive tank waste at the Hanford Site. Understanding gas generation and the ability to predict the gas generation rates are important for controlling the flammable gas hazard during interim storage and for planning for future activities such as waste transfer, retrieval, and treatment. Several models have been previously proposed to estimate the hydrogen generation rate but were limited by very little waste data. In this work, based on the availability of a large body of tank waste data, empirical rate equation models are developed and validated to simulate the hydrogen generation from thermal chemical reactions, water and organic radiolysis, and corrosion processes

  2. Continuous hydrogen generation from formic acid; Kontinuierliche Wasserstofferzeugung aus Ameisensaeure

    Energy Technology Data Exchange (ETDEWEB)

    Sponholz, Peter; Mellmann, Doerthe; Boddien, Albert; Gaertner, Felix; Junge, Henrik; Beller, Matthias [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse e.V.

    2011-07-01

    One of the biggest challenges in this century will be the sustainable supply of energy. A major goal is to meet the energy demand without using fossil fuels and to integrate renewable energy into the energy economy. For applications storage systems for hydrogen are needed. One possible storage system for hydrogen is formic acid which is liquid, non-toxic and has a gravimetric hydrogen content of 4.4%. Our aim is to continuously dehydrogenize formic acid and to use the gas mixture (H{sub 2}, CO{sub 2}) in a connected fuel cell. (orig.)

  3. Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

    Science.gov (United States)

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2015-07-14

    Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

  4. Hydrogen Generator by Methane Pyrolysis with Carbon Capture Project

    Data.gov (United States)

    National Aeronautics and Space Administration — ORBITEC proposes to develop, fabricate, and test a system to provide 99.999% hydrogen by efficiently performing methane pyrolysis. The system has three unique...

  5. NaBH4 generator integrated with energy conversion device based on hydrogen combustion

    Science.gov (United States)

    Netskina, O. V.; Fursenko, R. V.; Komova, O. V.; Odintsov, E. S.; Simagina, V. I.

    2015-01-01

    A thermoelectric energy conversion device operating on the heat generated by a hydrogen diffusion microflame has been developed. For the first time, a NaBH4 hydrogen generator has been employed as a source of fuel for such type of power generator. A 1%Ru-3%Co/Sibunit catalyst ensures hydrogen generation at a rate of 3 cm3 s-1 during 3 h. Power and efficiency characteristics of the integrated system consisting of a hydrogen generator and an energy converter based on combustion technologies have been studied experimentally. The total efficiency and the generated power of the system were measured to achieve values of up to 1.23% and 0.25 W, respectively. Ways to further improve the system's power output and efficiency characteristics have been discussed.

  6. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation.

    Science.gov (United States)

    Viswanathan, Venkatasubramanian; Hansen, Heine A; Nørskov, Jens K

    2015-11-01

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.

  7. Selective electrochemical generation of hydrogen peroxide from water oxidation

    CERN Document Server

    Viswanathan, Venkatasubramanian; Nørskov, Jens K

    2015-01-01

    Water is a life-giving source, fundamental to human existence, yet, over a billion people lack access to clean drinking water. Present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH$^*$ can be used as a descriptor to screen for selectivity trends between the 2e$^-$ water oxidation to H$_2$O$_2$ and the 4e$^-$ oxidation to O$_2$. We show that materials that bind oxygen intermediates sufficiently weakly, such as SnO$_2$, can activate hydrogen peroxide evolution. We present a rati...

  8. Robust and Porous β-Diketiminate-Functionalized Metal–Organic Frameworks for Earth-Abundant-Metal-Catalyzed C–H Amination and Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Thacker, Nathan C.; Lin, Zekai; Zhang, Teng; Gilhula, James C.; Abney, Carter W.; Lin, Wenbin (UC)

    2016-05-27

    We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity. Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.

  9. Effect of water injection on hydrogen generation during severe accident in PWR

    Institute of Scientific and Technical Information of China (English)

    TAO Jun; CAO Xuewu

    2009-01-01

    Effect of water injection on hydrogen generation during severe accident in a 1000 MWe pressurized water reactor was studied.The analyses were carried out with different water injection rates at different core damage stages.The core can be quenched and accident progression can be terminated by water injection at the time before cohesive core debris is formed at lower core region.Hydrogen generation rate decreases with water injection into the core at the peak core temperature of 1700 K,because the core is quenched and reflooded quickly.The water injection at the peak core temperature of 1900 K,the hydrogen generation rate increases at low injection rates of the water,as the core is quenched slowly and the core remains in uncovered condition at high temperatures for a longer time than the situation of high injection rate.At peak core temperature of 2100-2300 K,the Hydrogen generation rate increases by water injection because of the steam serving to the high temperature steam-starved core.Hydrogen generation rate increases significantly after water injection into the core at peak core temperature of 2500 K because of the steam serving to the relocating Zr-U-O mixture.Almost no hydrogen generation can be seen in base case after formation of the molten pool at the lower core region.However,hydrogen is generated if water is injected into the molten pool,because steam serves to the crust supporting the molten pool.Reactor coolant system (RCS) depressurization by opening power operated relief valves has important effect on hydrogen generation.Special attention should be paid to hydrogen generation enhancement caused by RCS depressurization.

  10. Hydrogen generation monitoring and mass gain analysis during the steam oxidation for Zircaloy using hydrogen and oxygen sensors

    International Nuclear Information System (INIS)

    The oxidation behavior of Zircaloy-4 at high temperatures in a flowing Ar-H2O (saturated at 323 K) mixed gas was investigated using hydrogen and oxygen sensors installed at a gas outlet, and the utility of the gas sensing methods by using both sensors was examined. The generated amount of hydrogen was determined from the hydrogen partial pressure continuously measured by the hydrogen sensor, and the resultant calculated oxygen amount that reacted with the specimen was in close agreement with the mass gain gravimetrically measured after the experiment. This result demonstrated that the hydrogen partial pressure measurement using a hydrogen sensor is an effective method for examining the steam oxidation of this metal as well as monitoring the hydrogen evolution. The advantage of this method is that the oxidation rate of the metal at any time as a differential quantity is able to be obtained, compared to the oxygen amount gravimetrically measured as an integral quantity. When the temperature was periodically changed in the range of 1173 K to 1523 K, highly accurate measurements could be carried out using this gas monitoring method, although reasonable measurements were not gravimetrically performed due to the fluctuating thermo-buoyancy during the experiment. A change of the oxidation rate was clearly detected at a monoclinic tetragonal transition temperature of ZrO2. From the calculation of the water vapor partial pressure during the thermal equilibrium condition using the hydrogen and oxygen partial pressures, it became clear that a thermal equilibrium state is maintained when the isothermal condition is maintained, but is not when the temperature increases or decreases with time. Based on these results, it was demonstrated that the gas monitoring system using hydrogen and oxygen sensors is very useful for investigating the oxidation process of the Zircaloy in steam. (author)

  11. In situ generation of hydrogen from water by aluminum corrosion in solutions of sodium aluminate

    OpenAIRE

    Soler Turu, Lluis; Candela Soto, Angélica Maria; Macanás de Benito, Jorge; Muñoz Tapia, Maria; Casado Giménez, Juan

    2009-01-01

    A new process to obtain hydrogen from water using aluminum in sodium aluminate solutions is described and compared with results obtained in aqueous sodium hydroxide. This process consumes only water and aluminum, which are raw materials much cheaper than other compounds used for in situ hydrogen generation, such as hydrocarbons and chemical hydrides, respectively. As a consequence, our process could be an economically feasible alternative for hydrogen to supply fuel cells. Results showed an i...

  12. Photocatalytic hydrogen generation using glycerol wastewater over Pt/TiO2

    Institute of Scientific and Technical Information of China (English)

    Min LI; Yuexiang LI; Shaoqin PENG; Gongxuan LU; Shuben LI

    2009-01-01

    Using glycerol as electron donor, photocataly-tic hydrogen generation over Pt/TiO2 was investigated.The results show that glycerol can not only improve the efficiency of photocatalytic hydrogen generation but can also be decomposed effectively. The factors which affect photocatalytic hydrogen generation, such as irradiation time, initial concentration of the glycerol solution, pH-value of the suspensions and the coexisting substances were studied. The final oxidation products of glycerol were H2O and CO2. Glyceraldhyde, glycoladehyde, glycolic acid and formaldehyde were identified as the intermedi-ates. A possible reaction mechanism was discussed.

  13. A new approach for hydrogen generation from sewage sludge.

    Science.gov (United States)

    Zhang, Qiwu; Kano, Junya

    2016-02-01

    A new process to produce hydrogen efficiently from sewage sludge (SWS) was developed with co-grinding operation of the dried SWS with calcium and nickel hydroxides (Ca(OH)2 and Ni(OH)2) and subsequent heating of the ground mixture at relatively low temperature below 600°C. A set of analytical methods were used to characterize the ground samples before heating and the gaseous and solid products after heating. Thermo-mass spectroscopic (TG-MS) analysis showed hydrogen occurrence around 450°C. Hydrogen yield over 70g per kg SWS with concentration of 93.6% was obtained with the hydroxide additions of Ca to C from SWS at 1:1 and Ni to C at 1:6, respectively. X-ray diffraction (XRD) analysis of the solid residues after heating confirmed the existences of calcium carbonate and nickel metal. Based on the obtained results, possible reaction pathway was proposed. PMID:26642224

  14. Hydrogen bonding strength of interfacial water determined with surface sum-frequency generation

    NARCIS (Netherlands)

    M. Sovago; R. Kramer Campen; H.J. Bakker; M. Bonn

    2009-01-01

    We demonstrate that marked variations exist in hydrogen bonding interactions of interfacial water at different aqueous interfaces. The average hydrogen bond strength and its distribution are inferred from surface sum-frequency generation (SFG) spectra through the center frequency and width, respecti

  15. Investment in hydrogen tri-generation for wastewater treatment plants under uncertainties

    Science.gov (United States)

    Gharieh, Kaveh; Jafari, Mohsen A.; Guo, Qizhong

    2015-11-01

    In this article, we present a compound real option model for investment in hydrogen tri-generation and onsite hydrogen dispensing systems for a wastewater treatment plant under price and market uncertainties. The ultimate objective is to determine optimal timing and investment thresholds to exercise initial and subsequent options such that the total savings are maximized. Initial option includes investment in a 1.4 (MW) Molten Carbonate Fuel Cell (MCFC) fed by mixture of waste biogas from anaerobic digestion and natural gas, along with auxiliary equipment. Produced hydrogen in MCFC via internal reforming, is recovered from the exhaust gas stream using Pressure Swing Adsorption (PSA) purification technology. Therefore the expansion option includes investment in hydrogen compression, storage and dispensing (CSD) systems which creates additional revenue by selling hydrogen onsite in retail price. This work extends current state of investment modeling within the context of hydrogen tri-generation by considering: (i) Modular investment plan for hydrogen tri-generation and dispensing systems, (ii) Multiple sources of uncertainties along with more realistic probability distributions, (iii) Optimal operation of hydrogen tri-generation is considered, which results in realistic saving estimation.

  16. Hydrogen generation from aluminium corrosion in reactor containment spray solutions

    International Nuclear Information System (INIS)

    The aluminium corrosion experiments in reactor containment spray solutions, under the conditions expected to prevail during LOCA in BWR and PWR, were performed in order to investigate relationships between temperature, pH and hydrogen production rates. In order to simulate the conditions in a BWR containment realistic ratios between aluminium surface and water volume and between aluminium surface and oxygen volume were used. Three different aluminium alloys were exposed to spray solutions: AA 1050, AA 5052 and AA 6082. The corrosion rates were measured for BWR solutions (deaerated and aerated) with pH 5 and 9 at 50, 100 and 1500C. The pressure was constantly 0.8 MPa. The hydrogen production rate was measured by means of gas chromatography. In deionized BWR water the corrosion rates did not exceed about 0.05 mm/year in all cases, i.e. were practically independent of temperature and pH. Hydrogen concentrations were less than 0.1 vol.% in cooled dry gas. Corrosion rates and hydrogen production in PWR alkaline solution measured at pH 9.7 and 1500C were very high. AA 5052 alloy was the best material

  17. Enzymatic generation of hydrogen peroxide shows promising antifouling effect

    DEFF Research Database (Denmark)

    Kristensen, J.B.; Olsen, Stefan Møller; Laursen, B.S.;

    2010-01-01

    The antifouling (AF) potential of hydrogen peroxide (H2O2) produced enzymatically in a coating containing starch, glucoamylase, and hexose oxidase was evaluated in a series of laboratory tests and in-sea field trials. Dissolved H2O2 inhibited bacterial biofilm formation by eight of nine marine Pr...

  18. Combustion of hydrogen-oxygen mixture in electrochemically generated nanobubbles

    NARCIS (Netherlands)

    Svetovoy, Vitaly B.; Sanders, Remco G.P.; Lammerink, Theo S.J.; Elwenspoek, Miko

    2011-01-01

    Ignition of exothermic chemical reactions in small volumes is considered as difficult or impossible due to the large surface-to-volume ratio. Here observation of the spontaneous reaction is reported between hydrogen and oxygen in bubbles whose diameter is smaller than a threshold value around 150 nm

  19. HOGEN{trademark} proton exchange membrane hydrogen generators: Commercialization of PEM electrolyzers

    Energy Technology Data Exchange (ETDEWEB)

    Smith, W.F.; Molter, T.M. [Proton Energy Systems, Inc., Rocky Hill, CT (United States)

    1997-12-31

    PROTON Energy Systems` new HOGEN series hydrogen generators are Proton Exchange Membrane (PEM) based water electrolyzers designed to generate 300 to 1000 Standard Cubic Feet Per Hour (SCFH) of high purity hydrogen at pressures up to 400 psi without the use of mechanical compressors. This paper will describe technology evolution leading to the HOGEN, identify system design performance parameters and describe the physical packaging and interfaces of HOGEN systems. PEM electrolyzers have served US and UK Navy and NASA needs for many years in a variety of diverse programs including oxygen generators for life support applications. In the late 1970`s these systems were advocated for bulk hydrogen generation through a series of DOE sponsored program activities. During the military buildup of the 1980`s commercial deployment of PEM hydrogen generators was de-emphasized as priority was given to new Navy and NASA PEM electrolysis systems. PROTON Energy Systems was founded in 1996 with the primary corporate mission of commercializing PEM hydrogen generators. These systems are specifically designed and priced to meet the needs of commercial markets and produced through manufacturing processes tailored to these applications. The HOGEN series generators are the first step along the path to full commercial deployment of PEM electrolyzer products for both industrial and consumer uses. The 300/1000 series are sized to meet the needs of the industrial gases market today and provide a design base that can transition to serve the needs of a decentralized hydrogen infrastructure tomorrow.

  20. A composite of borohydride and super absorbent polymer for hydrogen generation

    Science.gov (United States)

    Li, Z. P.; Liu, B. H.; Liu, F. F.; Xu, D.

    To develop a hydrogen source for underwater applications, a composite of sodium borohydride and super absorbent polymer (SAP) is prepared by ball milling sodium borohydride powder with SAP powder, and by dehydrating an alkaline borohydride gel. When sodium polyacrylate (NaPAA) is used as the SAP, the resulting composite exhibits a high rate of borohydride hydrolysis for hydrogen generation. A mechanism of hydrogen evolution from the NaBH 4-NaPAA composite is suggested based on structure analysis by X-ray diffraction and scanning electron microscopy. The effects of water and NiCl 2 content in the precursor solution on the hydrogen evolution behavior are investigated and discussed.

  1. Experimental and modelling evaluation of an ammonia-fuelled microchannel reactor for hydrogen generation / Steven Chiuta

    OpenAIRE

    Chiuta, Steven

    2015-01-01

    In this thesis, ammonia (NH3) decomposition was assessed as a fuel processing technology for producing on-demand hydrogen (H2) for portable and distributed fuel cell applications. This study was motivated by the present lack of infrastructure to generate H2 for proton exchange membrane (PEM) fuel cells. An overview of past and recent worldwide research activities in the development of reactor technologies for portable and distributed hydrogen generation via NH3 decomposition wa...

  2. Solar-Hydrogen-Fuel Cell Prototype as a Source of Renewable Energy Generation

    OpenAIRE

    Andrés Rodríguez-Castellanos; Ernesto López-Torres; Omar Solorza-Feria

    2007-01-01

    A small renewable energy prototype is presented, integrated by a solar photovoltaic module used for electrolysis of water where the resulting hydrogen was fed to a regenerative fuel cell for a clean electricity generation. A photovoltaic module provided DC power to an electrolyzer, to produce 56 cm3/min of hydrogen which is fed to a fuel cell and generate electricity. This prototype was designed and manufactured to show the future energy scenario of renewable energy. For water electrolysis, p...

  3. DESIGN, SYNTHESIS AND STUDY OF MULTI-COMPONENT AND INTEGRATED SYSTEMS FOR LIGHT-DRIVEN HYDROGEN GENERATION

    Energy Technology Data Exchange (ETDEWEB)

    Professor Richard Eisenberg

    2012-07-18

    The research focussed on fundamental problems in the conversion of light to stored chemical energy. Specifically, work was completed on the design, synthesis and study of multi-component super- and supramolecular systems for photoinduced charge separation, one of the key steps in artificial photosynthesis, and on the use of these and related systems for the photochemical generation of H2 from water. At the center of these systems are chromophores comprised of square planar coordinated Pt(II) ions with arylacetylide and either diimine or terpyridyl ligands. Previous work had shown that the chromophores are photoluminescent in fluid solution with long-lived metal-to-ligand charge transfer (3MLCT) excited states that are necessarily directional. An advance which set the stage for a number of proposed studies was the light-driven production of hydrogen from water using a Pt(terpyridyl)(arylacetylide)+ chromophore and a sacrificial electron donor. The reaction is catalytic and appears to rival previously reported ruthenium bipyridyl systems in terms of H2 production. Variation of system components and mechanistic studies were conducted to understand better the individual steps in the overall process and how to improve its efficiency. Success with light driven H2 generation was employed as a key probe as new systems were constructed consisting of triads for photoinduced charge separation placed in close proximity to the H2 generating catalyst - a Pt colloid - through direct linkage or supramolecular interactions with the polymer used to stabilize the colloid. In order to prepare new donor-chromophore-acceptor (D-C-A) triads and associated D-C and C-A dyads, new ligands were synthesized having functional groups for different coupling reactions such as simple amide formation and Pd-catalyzed coupling. In these systems, the donor was attached to the arylacetylide ligands and the acceptor was linked to the diimine or terpyridyl chelate. Research under the contract proved

  4. Methane decomposition under a corona discharge to generate COx-free hydrogen

    International Nuclear Information System (INIS)

    A non-thermal plasma reforming unit operating at atmospheric pressure has been developed for converting methane to COx-free hydrogen. Argon was used to provide additional electrons and photons for higher reaction rates. A series of experiments was performed for positive corona discharge at a fixed inter-electrode distance (15 mm) to study the effects of discharge power (range of 14–20 W) and residence time (60, 120, 180 and 240 s). A second series of experiments studied the effect of inter-electrode distance on hydrogen production, with distances of 15, 20, 25, 30 and 35 mm tested. The analysis of the results shows that both discharge power and residence time, have a positive influence on methane conversion, hydrogen selectivity and energy conversion efficiency. Longer discharge gaps favour hydrogen production. A final series of experiments on corona polarity showed that a positive discharge was preferable. - Highlights: • We examine plasma-assisted COx-free hydrogen generation from methane. • Higher powers and residence times favour hydrogen production. • Positive polarity and higher inter-electrode distances favour hydrogen production. • Energy conversion efficiency is mainly governed by hydrogen selectivity. • Corona discharges are a promising approach for hydrogen generation from methane

  5. Muon Catalyzed Fusion

    Science.gov (United States)

    Armour, Edward A.G.

    2007-01-01

    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  6. Generation of Hydrogen from Photolysis of Organic Acids by Photosynthetic Bacteria

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Photodecomposition of ten kinds of organic acids by Rhodopseudomonas palustris for producing hydrogen has been investigated. By using acetate as hydrogen donor, dynamics of hydrogen production and cell growth has been determined; the influences of acetate concentration, temperature, light intensity and the effects of the interaction among metal ions (Fe3+, Ni2+), acetate and glutamate in aqueous solution on hydrogen production have been examined for optimizing the conditions of H2 generation. The results show that H2 production is partially correlated with cell growth; Ni2+ inhibits hydrogen production, but enhances cell growth; Fe3+ promotes hydrogen production evidently. The highest rate of H2 production is 22.1 mL L-1 h-1 under the conditions of 35 ~ 37℃, 6000 ~ 8000 lx, 30 mmolL-1 of acetate, 9 mmolL-1 of glutamate, and 50 (molL-1 of Fe3+.

  7. Hydrogen generation through massive corrosion of deformed aluminum in water

    Energy Technology Data Exchange (ETDEWEB)

    Czech, E.; Troczynski, T. [Materials Engineering Department, University of British Columbia, 309-6350 Stores Rd., Vancouver, BC V6T 1Z4 (Canada)

    2010-02-15

    Aluminum, one of most reactive metals, rapidly corrodes in strong acidic or alkaline solutions but passivates at pH of about 5-9. We have determined that the passivation of aluminum in this range of pH, and in particular in regular tap water, can be substantially prevented after milling of aluminum with water-soluble inorganic salts (referred to as ''WIS''), such as KCl or NaCl. Ensuing corrosion of Al in tap water, with accompanying release of hydrogen and precipitation of aluminum hydroxide, at normal pressure and moderate temperatures ({proportional_to}55 C) is rapid and substantial. For example, {proportional_to}92% of the Al in the Al-WIS system when milled for 1 h and {proportional_to}81% when milled for 15 min, corrodes in 1 h, with the release of 1.5 mol of hydrogen per each mole of Al consumed in the reaction. Besides gaseous hydrogen, only solid aluminum hydroxides were formed as the reaction byproducts, opening up the possibility of straightforward recycling of the system. The effects of WIS concentration, chemistry of other additives, powder particle size, temperature, and milling conditions on the reaction kinetics are reported. (author)

  8. Microsecond X-ray Absorption Spectroscopy Identification of Co(I) Intermediates in Cobaloxime-Catalyzed Hydrogen Evolution.

    Science.gov (United States)

    Smolentsev, Grigory; Cecconi, Bianca; Guda, Alexander; Chavarot-Kerlidou, Murielle; van Bokhoven, Jeroen A; Nachtegaal, Maarten; Artero, Vincent

    2015-10-19

    Rational development of efficient photocatalytic systems for hydrogen production requires understanding the catalytic mechanism and detailed information about the structure of intermediates in the catalytic cycle. We demonstrate how time-resolved X-ray absorption spectroscopy in the microsecond time range can be used to identify such intermediates and to determine their local geometric structure. This method was used to obtain the solution structure of the Co(I) intermediate of cobaloxime, which is a non-noble metal catalyst for solar hydrogen production from water. Distances between cobalt and the nearest ligands including two solvent molecules and displacement of the cobalt atom out of plane formed by the planar ligands have been determined. Combining in situ X-ray absorption and UV/Vis data, we demonstrate how slight modification of the catalyst structure can lead to the formation of a catalytically inactive Co(I) state under similar conditions. Possible deactivation mechanisms are discussed. PMID:26388205

  9. Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

    Science.gov (United States)

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2015-08-11

    Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

  10. Understanding the Mechanism of the Hydrogen Abstraction from Arachidonic Acid Catalyzed by the Human Enzyme 15-Lipoxygenase-2. A Quantum Mechanics/Molecular Mechanics Free Energy Simulation.

    Science.gov (United States)

    Suardíaz, Reynier; Jambrina, Pablo G; Masgrau, Laura; González-Lafont, Àngels; Rosta, Edina; Lluch, José M

    2016-04-12

    Lipoxygenases (LOXs) are a family of enzymes involved in the biosynthesis of several lipid mediators. In the case of human 15-LOX, the 15-LOX-1 and 15-LOX-2 isoforms show slightly different reaction regiospecificity and substrate specificity, indicating that substrate binding and recognition may be different, a fact that could be related to their different biological role. Here, we have used long molecular dynamics simulations, QM(DFT)/MM potential energy and free energy calculations (using the newly developed DHAM method), to investigate the binding mode of the arachidonic acid (AA) substrate into 15-LOX-2 and the rate-limiting hydrogen-abstraction reaction 15-LOX-2 catalyzes. Our results strongly indicate that hydrogen abstraction from C13 in 15-LOX-2 is only consistent with the "tail-first" orientation of AA, with its carboxylate group interacting with Arg429, and that only the pro-S H13 hydrogen will be abstracted (being the pro-R H13 and H10 too far from the acceptor oxygen atom). At the B3LYP/6-31G(d) level the potential and free energy barriers for the pro-S H13 abstraction of AA by 15-LOX-2 are 18.0 and 18.6 kcal/mol, respectively. To analyze the kinetics of the hydrogen abstraction process, we determined a Markov model corresponding to the unbiased simulations along the state-discretized reaction coordinate. The calculated rates based on the second largest eigenvalue of the Markov matrices agree well with experimental measurements, and also provide the means to directly determine the pre-exponential factor for the reaction by comparing with the free energy barrier height. Our calculated pre-exponential factor is close to the value of kBT/h. On the other hand, our results suggest that the spin inversion of the complete system (including the O2 molecule) that is required to happen at some point along the full process to lead to the final hydroperoxide product, is likely to take place during the hydrogen transfer, which is a proton coupled electron transfer

  11. Tandem hydrogenation and condensation of fluorinated α,β-unsaturated ketones with primary amines, catalyzed by nickel.

    Science.gov (United States)

    Castellanos-Blanco, Nahury; Flores-Alamo, Marcos; García, Juventino J

    2015-09-21

    A simple homogeneous catalytic system based on nickel phosphine complexes has been developed for the transfer hydrogenation and condensation of α,β-unsaturated ketones to yield saturated ones and saturated imines using primary amines as hydrogen donors. Thus, a wide range of fluorinated 1,5-diaryl-1,4-pentadiene-3-ones were allowed to react with substituted benzylamines in the presence of [(dippe)Ni(μ-H)]2 (dippe = 1,2-bis-(diisopropylphosphino)-ethane) using ethanol as a solvent at 180 °C to give the corresponding saturated carbonyl compounds; here hydrogenation of the C[double bond, length as m-dash]C bond was preferred over the C[double bond, length as m-dash]O bond. Under the same reaction conditions but using an excess of benzylamine, a tandem process is then favoured, starting also with the reduction of the C[double bond, length as m-dash]C bond followed by a nucleophilic addition of the primary amine to yield valuable saturated imines with good to excellent yields (62%-91%). PMID:26250992

  12. Development of generator-cooling hydrogen purity improvement system using hydrogen absorbing alloy; Suiso kyuzo gokin ni yoru hatsudenkinai suiso jundo kojo system no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Nishimura, Y.; Sato, J.; Haruki, N.; Kogi, T.; Okuno, Y. [The Kansai Electric Power Co. Inc., Osaka (Japan); Takeda, H.; Wakisaka, Y. [The Japan Steel Works, Ltd., Tokyo (Japan); Fujita, T. [Mitsubishi Electric Corp., Tokyo (Japan)

    1997-01-31

    A generator-cooling hydrogen purity improvement system was developed by utilizing hydrogen absorbing and discharging functions of hydrogen storage alloy. For demonstration test with an actual machine, four elements, Ca, Ni, Mm and Al, were used as hydrogen storage alloys. To treat hydrogen gas with a wide range of purity and reduce hydrogen gas feed, flow operation for hydrogen purity improvement, batch operation, and recycle operation for maintaining the hydrogen purity were performed. As a result of the generator-cooling hydrogen purity improvement demonstration test, it was found that the hydrogen purity can be enhanced from 97.69% before operation to 99.9% after operation for 104 hours and to 99.95% after operation for 140 hours. The hydrogen recovery rates during flow test and batch test were between 92 and 95%. For the hydrogen purity maintaining test, it was confirmed that the high hydrogen purity of 99.9% has been continuously maintained for 140 days, and that the hydrogen recovery rate was over 99%. 2 refs., 15 figs., 3 tabs.

  13. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.

    2015-01-01

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized...... sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively....

  14. CATALYTIC INTERACTIONS OF RHODIUM, RUTHENIUM, AND MERCURY DURING SIMULATED DWPF CPC PROCESSING WITH HYDROGEN GENERATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-10-09

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell (CPC) vessels were performed as part of the ongoing investigation into catalytic hydrogen generation. Rhodium, ruthenium, and mercury have been identified as the principal elemental factors affecting the peak hydrogen generation rate in the DWPF Sludge Receipt and Adjustment Tank (SRAT) for a given acid addition. The primary goal of this study is to identify any significant interactions between the three factors. Noble metal concentrations were similar to recent sludge batches. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%. An experimental matrix was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), two duplicate midpoint runs, and two additional replicate runs to assess reproducibility away from the midpoint. Midpoint testing can identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. Six Slurry Mix Evaporator (SME) cycles were performed to supplement the SME hydrogen generation database. Some of the preliminary findings from this study include: (1) Rh was linked to the maximum SRAT hydrogen generation rate in the first two hours after acid addition in preliminary statistical modeling. (2) Ru was linked conclusively to the maximum SRAT hydrogen generation rate in the last four hours of reflux in preliminary statistical modeling. (3) Increasing the ratio of Hg/Rh shifted the noble metal controlling the maximum SRAT hydrogen generation rate from

  15. Zircaloy-oxidation and hydrogen-generation rates in degraded-core accident situations

    International Nuclear Information System (INIS)

    Oxidation of Zircaloy cladding is the primary source of hydrogen generated during a degraded-core accident. In this paper, reported Zircaloy oxidation rates, either measured at 1500 to 18500C or extrapolated from the low-temperature data obtained at 0C, are critically reviewed with respect to their applicability to a degraded-core accident situation in which the high-temperature fuel cladding is likely to be exposed to and oxidized in mixtures of hydrogen and depleted steam, rather than in an unlimited flux of pure steam. New results of Zircaloy oxidation measurements in various mixtures of hydrogen and steam are reported for >15000C. The results show significantly smaller oxidation and, hence, hydrogen-generation rates in the mixture, compared with those obtained in pure steam. It is also shown that a significant fraction of hydrogen, generated as a result of Zircaloy oxidation, is dissolved in the cladding material itself, which prevents that portion of hydrogen from reaching the containment building space. Implications of these findings are discussed in relation to a more realistic method of quantifying the hydrogen source term for a degraded-core accident analysis

  16. Control of microbially generated hydrogen sulfide in produced waters

    Energy Technology Data Exchange (ETDEWEB)

    Burger, E.D.; Vance, I.; Gammack, G.F.; Duncan, S.E.

    1995-12-31

    Production of hydrogen sulfide in produced waters due to the activity of sulfate-reducing bacteria (SRB) is a potentially serious problem. The hydrogen sulfide is not only a safety and environmental concern, it also contributes to corrosion, solids formation, a reduction in produced oil and gas values, and limitations on water discharge. Waters produced from seawater-flooded reservoirs typically contain all of the nutrients required to support SRB metabolism. Surface processing facilities provide a favorable environment in which SRB flourish, converting water-borne nutrients into biomass and H{sub 2}S. This paper will present results from a field trial in which a new technology for the biochemical control of SRB metabolism was successfully applied. A slip stream of water downstream of separators on a produced water handling facility was routed through a bioreactor in a side-steam device where microbial growth was allowed to develop fully. This slip stream was then treated with slug doses of two forms of a proprietary, nonbiocidal metabolic modifier. Results indicated that H{sub 2}S production was halted almost immediately and that the residual effect of the treatment lasted for well over one week.

  17. Ruthenium(0)-catalyzed hydroarylation of alkynes via ketone-directed C-H functionalization using in situ-generated ruthenium complexes.

    Science.gov (United States)

    Hu, Feng; Szostak, Michal

    2016-08-11

    A versatile method for the Ru(0)-catalyzed hydroarylation of alkynes using weakly-coordinating ketones enabled by the in situ generation of a Ru(0) catalyst from an air-stable, inexpensive and user-friendly Ru(ii) precatalyst is reported for the first time. The method provides straightforward access to a wide range of functionalized ketone building blocks that would be difficult to access by conventional methods. Most crucially, this report demonstrates for the first time that the in situ generated Ru(0) catalysts advance the classic Ru(0)-catalyzed C-H functionalization platform to substrates that would otherwise be unreactive. Product manipulation and mechanistic studies are reported. PMID:27411592

  18. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    Energy Technology Data Exchange (ETDEWEB)

    T. Brent Gunnoe

    2011-02-17

    , which has provided a comprehensive understanding of the impact of steric and electronic parameters of 'L' on the catalytic hydroarylation of olefins. (3) We have completed and published a detailed mechanistic study of stoichiometric aromatic C-H activation by TpRu(L)(NCMe)Ph (L = CO or PMe{sub 3}). These efforts have probed the impact of functionality para to the site of C-H activation for benzene substrates and have allowed us to develop a detailed model of the transition state for the C-H activation process. These results have led us to conclude that the C-H bond cleavage occurs by a {sigma}-bond metathesis process in which the C-H transfer is best viewed as an intramolecular proton transfer. (4) We have completed studies of Ru complexes possessing the N-heterocyclic carbene IMes (IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene). One of these systems is a unique four-coordinate Ru(II) complex that catalyzes the oxidative hydrophenylation of ethylene (in low yields) to produce styrene and ethane (utilizing ethylene as the hydrogen acceptor) as well as the hydrogenation of olefins, aldehydes and ketones. These results provide a map for the preparation of catalysts that are selective for oxidative olefin hydroarylation. (5) The ability of TpRu(PMe{sub 3})(NCMe)R systems to activate sp{sup 3} C-H bonds has been demonstrated including extension to subsequent C-C bond forming steps. These results open the door to the development of catalysts for the functionalization of more inert C-H bonds. (6) We have discovered that Pt(II) complexes supported by simple nitrogen-based ligands serve as catalysts for the hydroarylation of olefins. Given the extensive studies of Pt-based catalytic C-H activation, we believe these results will provide an entry point into an array of possible catalysts for hydrocarbon functionalization.

  19. Three-component, one-pot synthesis of benzo[f]indenoquinoline derivatives catalyzed by poly(4-vinylpyridinium) hydrogen sulfate

    Institute of Scientific and Technical Information of China (English)

    Nader Ghaffari Khaligh

    2014-01-01

    7-Aryl-8H-benzo[f]indeno[2,1-b]quinoline-8-one derivatives were synthesized by means of a one-pot condensation of 2-naphthylamine, aromatic aldehydes, and indane-1,3-dione in ethanol under refluxing conditions in the presence of poly(4-vinylpyridinium) hydrogen sulfate, a solid acid catalyst. This method has the advantages of high yield, clean reaction, simple methodology, and short reaction time. The catalyst could be recycled and reused four times without significant loss of activity. The structure of the novel compounds was confirmed by IR, 1H NMR, and 13C NMR spec-troscopy and elemental analysis.

  20. Enantio- and Periselective Nitroalkene Diels-Alder Reactions Catalyzed by Helical-Chiral Hydrogen Bond Donor Catalysts

    Directory of Open Access Journals (Sweden)

    Zhili Peng

    2013-08-01

    Full Text Available Helical-chiral double hydrogen bond donor catalysts promote the nitroalkene Diels-Alder reaction in an enantio- and periselective manner. This represents the first asymmetric catalytic nitroalkene Diels-Alder reaction via LUMO-lowering catalysis. To gain an insight into this new process, the substrate scope of our catalyst was investigated by exploiting readily available 5-substituted pentamethylcyclopentadienes. The catalyst was found to tolerate dienes with different steric demands as well as dienes substituted with heteroatoms. The synthetic utility of 5-substituted pentamethylcyclopentadienes is rather limited, and thus we have developed a three-step route to 1,4,5,5-tetrasubstituted cyclopentadienes from commercially available ketones.

  1. Enantio- and periselective nitroalkene Diels-Alder reactions catalyzed by helical-chiral hydrogen bond donor catalysts.

    Science.gov (United States)

    Peng, Zhili; Narcis, Maurice J; Takenaka, Norito

    2013-01-01

    Helical-chiral double hydrogen bond donor catalysts promote the nitroalkene Diels-Alder reaction in an enantio- and periselective manner. This represents the first asymmetric catalytic nitroalkene Diels-Alder reaction via LUMO-lowering catalysis. To gain an insight into this new process, the substrate scope of our catalyst was investigated by exploiting readily available 5-substituted pentamethylcyclopentadienes. The catalyst was found to tolerate dienes with different steric demands as well as dienes substituted with heteroatoms. The synthetic utility of 5-substituted pentamethylcyclopentadienes is rather limited, and thus we have developed a three-step route to 1,4,5,5-tetrasubstituted cyclopentadienes from commercially available ketones. PMID:23966083

  2. Empirical rate equation model and rate calculations of hydrogen generation for Hanford tank waste; FINAL

    International Nuclear Information System (INIS)

    Empirical rate equations are derived to estimate hydrogen generation based on chemical reactions, radiolysis of water and organic compounds, and corrosion processes. A comparison of the generation rates observed in the field with the rates calculated for twenty eight tanks shows agreement with in a factor of two to three

  3. Efficient Synthesis of Functionalized 1-oxo-1-phenyl-2-acetic Acids through Ru(II)-catalyzed Transfer Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaowei; Gong, Binwei; Meng, Yanqiu [Shenyang Univ. of Chemical Technology, Shenyang (Korea, Republic of); Yan, Yunnan [Gannan Medical Univ., Ganzhou (Korea, Republic of); Tang, Xiaobo; Eric Xu, H.; Yi, Wei [Chinese Academy of Sciences, Shanghai (China); Li, Qiu [Univ. of Science and Technology of China, Suzhou (China)

    2013-10-15

    A new and alternative method for the efficient synthesis of indanylacetic acid 2 has been developed. The methodology used RuCl(p-cymene)[(R,R)-TsDPEN] as the catalyst and formic acid-triethylamine as the hydrogen source at room temperature under solvent-free conditions, and the reactions have excellent chemoselectivity and good compatibility of substrates. Used our developed method as the starting step, gram scale synthesis of GR24 was achieved smoothly with an overall yield of 72%. All the results suggested that further development of such methodology may be of interest. Further work to establish the mechanistic reasons for selectivity and to further explore the synthetic scope of this mode of transfer hydrogenation is in progress. The synthetic SL analog, GR24 is a very potent germination stimulant, which is widely used in parasitic weed research to stimulate germination and as a standard for comparison of new germinating agents. Owing to the prevalence of GR24, its total synthesis constitutes a hot area of research. So far all known synthetic routes of GR24 used indanylacetic acid 2 as a key intermediate, for which very few methods of building compound 2 have been reported.

  4. Electrolysis of ammonia for hydrogen production catalyzed by Pt and Pt-Ir deposited on nickel foam

    Institute of Scientific and Technical Information of China (English)

    Min; Jiang; Dandan; Zhu; Xuebo; Zhao

    2014-01-01

    Electrolysis of ammonia in alkaline electrolyte solution was applied for the production of hydrogen. Both Pt-loaded Ni foam and Pt-Ir loaded Ni foam electrodes were prepared by electrodeposition and served as anode and cathode in ammonia electrolytic cell, respectively. The electrochemical behaviors of ammonia in KOH solution were individually investigated via cyclic voltammetry on three electrodes, i.e. bare Ni foam electrode, Pt-loaded Ni foam electrode and Pt-Ir loaded Ni foam electrode. The morphology and composition of the prepared Ni foam electrode were analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Effects of the concentration of electrolyte solution and temperature of electrolytic cell on the electrolysis reaction were examined in order to enhance the efficiency of ammonia electrolysis. The competition of ammonia electrolysis and water electrolysis in the same alkaline solution was firstly proposed to explain the changes of cell voltage with the electrolysis proceeding. At varying current densities, different cell voltages could be obtained from galvanostatic curves.The low cell voltage of 0.58 V, which is less than the practical electrolysis voltage of water(1.6 V), can be obtained at a current density of2.5 mA/cm2. Based on some experimental parameters, such as the applied current, the resulting cell voltage and output of hydrogen gas, the power consumption per gram of H2produced can be estimated.

  5. Hydrogen generation from steam reforming of ethanol in dielectric barrier discharge

    Institute of Scientific and Technical Information of China (English)

    Baowei Wang; Yijun Lü; Xu Zhang; Shuanghui Hu

    2011-01-01

    Dielectric barrier discharge(DBD)was used for the generation of hydrogen from ethanol reforming.Effects of reaction conditions,such as vaporization temperature,ethanol flow rate,water/ethanol ratio,and addition of oxygen,on the ethanol conversion and hydrogen yield,were studied.The results showed that the increase of ethanol flow rate decreased ethanol conversion and hydrogen yield,and high water/ethanol ratio and addition of oxygen were advantageous.Ethanol conversion and hydrogen yield increased with the vaporization room temperature up to the maximum at first,and then decreased slightly.The maximum hydrogen yield of 31.8% was obtained at an ethanol conversion of 88.4% under the optimum operation conditions of vaporization room temperature of 120℃,ethanol flux of 0.18 mL/min,water/ethanol ratio of 7.7 and oxygen volume concentration of 13.3%.

  6. Hydrogen generation by nuclear power for sustainable development in the 21-st century

    International Nuclear Information System (INIS)

    Hydrogen is the main non-polluting fuel. It is produced by natural gas steam reforming, water electrolysis and thermonuclear processes. Currently, 4% of the hydrogen world production is obtained by water electrolysis. The use of nuclear power for hydrogen production avoids the generation of greenhouse gases and the dependence of primary external energy sources. The US is currently developing a modular reactor for hydrogen production and water desalination, STAR - H2 (Secure Transportable Autonomous Reactor for Hydrogen production) with fast neutrons, lead cooling and passive safety systems operating at a temperature of 780 deg C. Also, a Russian reactor of the same type is operated at 540 deg C. China and India joint industrial countries like France, Japan, Russia and US in recognizing that any strategies aiming at a future with clean energy implies the nuclear energy

  7. CHALLENGES IN GENERATING HYDROGEN BY HIGH TEMPERATURE ELECTROLYSIS USING SOLID OXIDE CELLS

    Energy Technology Data Exchange (ETDEWEB)

    M. S. Sohal; J. E. O' Brien; C. M. Stoots; M. G. McKellar; J. S. Herring; E. A. Harvego

    2008-03-01

    Idaho National Laboratory’s (INL) high temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells is presented in this paper. The research results reported here have been obtained in a laboratory-scale apparatus. These results and common scale-up issues also indicate that for the technology to be successful in a large industrial setting, several technical, economical, and manufacturing issues have to be resolved. Some of the issues related to solid oxide cells are stack design and performance optimization, identification and evaluation of cell performance degradation parameters and processes, integrity and reliability of the solid oxide electrolysis (SOEC) stacks, life-time prediction and extension of the SOEC stack, and cost reduction and economic manufacturing of the SOEC stacks. Besides the solid oxide cells, balance of the hydrogen generating plant also needs significant development. These issues are process and ohmic heat source needed for maintaining the reaction temperature (~830°C), high temperature heat exchangers and recuperators, equal distribution of the reactants into each cell, system analysis of hydrogen and associated energy generating plant, and cost optimization. An economic analysis of this plant was performed using the standardized H2A Analysis Methodology developed by the Department of Energy (DOE) Hydrogen Program, and using realistic financial and cost estimating assumptions. The results of the economic analysis demonstrated that the HTE hydrogen production plant driven by a high-temperature helium-cooled nuclear power plant can deliver hydrogen at a cost of $3.23/kg of hydrogen assuming an internal rate of return of 10%. These issues need interdisciplinary research effort of federal laboratories, solid oxide cell manufacturers, hydrogen consumers, and other such stakeholders. This paper discusses research and development accomplished by INL on such issues and highlights associated challenges that need to

  8. Hydrogenation vs. H-D isotope scrambling during the conversion of ethylene with hydrogen/deuterium catalyzed by platinum under single-collision conditions.

    Science.gov (United States)

    Dong, Yujung; Ebrahimi, Maryam; Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

    2016-07-28

    The catalytic hydrogenation of olefins promoted by transition metals, represented here by the conversion of ethylene with platinum, was studied under a unique regime representing pressures in the mTorr range and single-collision conditions. Isotope labeling was used to follow the concurrent H-D exchange steps that occur during this conversion. Multiple isotope substitutions were observed in the resulting ethane products, reflecting the operability of the reversible stepwise mechanism proposed a long time ago by Horiuti and Polanyi. In fact, the ethane isotopologue distributions obtained in these experiments reflect a much higher probability for the dehydrogenation of ethyl intermediates back to the olefin, relative to the hydrogenation to ethane, than typically seen in this catalysis. In addition, a second mechanistic pathway was clearly identified, responsible for most of the dideuteroethane produced. Based on the dependence of the rates of formation of each isotopologue on the fluxes of deuterium and ethylene, it is argued that this second route may be a "reverse" Eley-Rideal step between gas-phase ethylene and two deuterium atoms adsorbed on adjacent sites of the platinum surface. The clear identification of this second pathway is new, and was possible thanks to our ability to explore a new single-collision intermediate pressure regime. PMID:27373226

  9. Hydrogenation vs. H-D isotope scrambling during the conversion of ethylene with hydrogen/deuterium catalyzed by platinum under single-collision conditions.

    Science.gov (United States)

    Dong, Yujung; Ebrahimi, Maryam; Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

    2016-07-28

    The catalytic hydrogenation of olefins promoted by transition metals, represented here by the conversion of ethylene with platinum, was studied under a unique regime representing pressures in the mTorr range and single-collision conditions. Isotope labeling was used to follow the concurrent H-D exchange steps that occur during this conversion. Multiple isotope substitutions were observed in the resulting ethane products, reflecting the operability of the reversible stepwise mechanism proposed a long time ago by Horiuti and Polanyi. In fact, the ethane isotopologue distributions obtained in these experiments reflect a much higher probability for the dehydrogenation of ethyl intermediates back to the olefin, relative to the hydrogenation to ethane, than typically seen in this catalysis. In addition, a second mechanistic pathway was clearly identified, responsible for most of the dideuteroethane produced. Based on the dependence of the rates of formation of each isotopologue on the fluxes of deuterium and ethylene, it is argued that this second route may be a "reverse" Eley-Rideal step between gas-phase ethylene and two deuterium atoms adsorbed on adjacent sites of the platinum surface. The clear identification of this second pathway is new, and was possible thanks to our ability to explore a new single-collision intermediate pressure regime.

  10. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

    KAUST Repository

    Shinagawa, Tatsuya

    2015-01-01

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.

  11. Hydrogen Fuel Cell Analysis: Lessons Learned from Stationary Power Generation Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Scott E. Grasman; John W. Sheffield; Fatih Dogan; Sunggyu Lee; Umit O. Koylu; Angie Rolufs

    2010-04-30

    This study considered opportunities for hydrogen in stationary applications in order to make recommendations related to RD&D strategies that incorporate lessons learned and best practices from relevant national and international stationary power efforts, as well as cost and environmental modeling of pathways. The study analyzed the different strategies utilized in power generation systems and identified the different challenges and opportunities for producing and using hydrogen as an energy carrier. Specific objectives included both a synopsis/critical analysis of lessons learned from previous stationary power programs and recommendations for a strategy for hydrogen infrastructure deployment. This strategy incorporates all hydrogen pathways and a combination of distributed power generating stations, and provides an overview of stationary power markets, benefits of hydrogen-based stationary power systems, and competitive and technological challenges. The motivation for this project was to identify the lessons learned from prior stationary power programs, including the most significant obstacles, how these obstacles have been approached, outcomes of the programs, and how this information can be used by the Hydrogen, Fuel Cells & Infrastructure Technologies Program to meet program objectives primarily related to hydrogen pathway technologies (production, storage, and delivery) and implementation of fuel cell technologies for distributed stationary power. In addition, the lessons learned address environmental and safety concerns, including codes and standards, and education of key stakeholders.

  12. Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN 3P ruthenium pincer complex under base-free Conditions

    KAUST Repository

    He, Lipeng

    2012-03-01

    A dearomatized complex [RuH(PN 3P)(CO)] (PN 3PN, N′-bis(di-tert-butylphosphino)-2,6-diaminopyridine) (3) was prepared by reaction of the aromatic complex [RuH(Cl)(PN 3P)(CO)] (2) with t-BuOK in THF. Further treatment of 3 with formic acid led to the formation of a rearomatized complex (4). These new complexes were fully characterized and the molecular structure of complex 4 was further confirmed by X-ray crystallography. In complex 4, a distorted square-pyramidal geometry around the ruthenium center was observed, with the CO ligand trans to the pyridinic nitrogen atom and the hydride located in the apical position. The dearomatized complex 3 displays efficient catalytic activity for hydrogen transfer of ketones in isopropanol. © 2011 Elsevier B.V. All rights reserved.

  13. Preparation and immobilization of diNOsarcobalt(III complex in zeolite y for the catalyzed production of hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    José G. Carriazo

    2013-01-01

    Full Text Available A complex cation, diNOsarcobalt(III, [Co(diNOsar]3+, (diNOsar = 1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo-[6.6.6]eicosane, was synthesized and immobilized in the cavities of a Y zeolite by the reaction of precursor species in the pores of the zeolite. The encapsulated material was compared to the compound diNOsarcobalt(III chloride, [Co(diNOsar]Cl3. Both diNOsarcobalt(III chloride and the zeolite-encapsulated complex, [Co(diNOsar]3+/zeolite, were obtained in high yield and characterized by ultraviolet-visible and infrared spectroscopy. X-ray diffraction demonstrated the incorporation of the complex cation into the pores of the zeolite. The catalytic production of hydrogen peroxide from oxygenated water confirmed the successful synthesis of the complex diNOsarcobalt(III immobilized in the zeolite.

  14. Effect of hydrogen on generation of lattice defects in shock-loaded Pd

    Energy Technology Data Exchange (ETDEWEB)

    Melikhova, Oksana, E-mail: oksivmel@yahoo.com [Charles University in Prague, Faculty of Mathematics and Physics, V Holešovičkách 2, CZ-180 00 Praha 8 (Czech Republic); Čížek, Jakub [Charles University in Prague, Faculty of Mathematics and Physics, V Holešovičkách 2, CZ-180 00 Praha 8 (Czech Republic); Chen, Yuzeng [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, 710072 Xi’an (China); Suo, Tao [School of Aeronautics, Northwestern Polytechnical University, 710072 Xi’an (China); Procházka, Ivan [Charles University in Prague, Faculty of Mathematics and Physics, V Holešovičkách 2, CZ-180 00 Praha 8 (Czech Republic); Liu, Feng [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, 710072 Xi’an (China)

    2015-10-05

    Highlights: • Influence of hydrogen on defect generation during shock-loading of Pd was examined. • Shock-loading introduced dislocations and vacancies. • Deformation-induced vacancies agglomerated into clusters consisting of 2–3 vacancies. • Absorbed hydrogen facilitates generation of both dislocations and vacancies. - Abstract: The effect of hydrogen absorbed in fcc Pd lattice on the generation of dislocations and vacancies during plastic deformation by shock-loading was investigated in this work. Well annealed bulk Pd samples were firstly charged with hydrogen up to various hydrogen concentrations. Subsequently the samples were shock-loaded on a Split-Hopkinson apparatus. Shock-loading yields extremely high strain rate and causes intensive plastic deformation of the samples. Lattice defects of the shock-loaded samples were characterized by positron lifetime spectroscopy combined with X-ray diffraction. It was found that shock-loaded Pd samples exhibit not only high density of dislocations but also small vacancy clusters created by agglomeration of deformation-induced vacancies. Pre-charging of Pd samples with hydrogen increases both the dislocation density and the concentration of vacancy clusters.

  15. Lessons learned from hydrogen generation and burning during the TMI-2 event

    International Nuclear Information System (INIS)

    This document summarizes what has been learned from generation of hydrogen in the reactor core and the hydrogen burn that occurred in the containment building of the Three Mile Island Unit No. 2 (TMI-2) nuclear power plant on March 28, 1979. During the TMI-2 loss-of-coolant accident (LOCA), a large quantity of hydrogen was generated by a zirconium-water reaction. The hydrogen burn that occurred 9 h and 50 min after the initiation of the TMI-2 accident went essentially unnoticed for the first few days. Even through the burn increased the containment gas temperature and pressure to 12000F (6500C) and 29 lb/in2 (200 kPa) gage, there was no serious threat to the containment building. The processes, rates, and quantities of hydrogen gas generated and removed during and following the LOCA are described in this report. In addition, the methods which were used to define the conditions that existed in the containment building before, during, and after the hydrogen burn are described. The results of data evaluations and engineering calculations are presented to show the pressure and temperature histories of the atmosphere in various containment segments during and after the burn. Material and equipment in reactor containment buildings can be protected from burn damage by the use of relatively simple enclosures or insulation

  16. High Performance, Low Cost Hydrogen Generation from Renewable Energy

    Energy Technology Data Exchange (ETDEWEB)

    Ayers, Katherine [Proton OnSite; Dalton, Luke [Proton OnSite; Roemer, Andy [Proton OnSite; Carter, Blake [Proton OnSite; Niedzwiecki, Mike [Proton OnSite; Manco, Judith [Proton OnSite; Anderson, Everett [Proton OnSite; Capuano, Chris [Proton OnSite; Wang, Chao-Yang [Penn State University; Zhao, Wei [Penn State University

    2014-02-05

    Renewable hydrogen from proton exchange membrane (PEM) electrolysis is gaining strong interest in Europe, especially in Germany where wind penetration is already at critical levels for grid stability. For this application as well as biogas conversion and vehicle fueling, megawatt (MW) scale electrolysis is required. Proton has established a technology roadmap to achieve the necessary cost reductions and manufacturing scale up to maintain U.S. competitiveness in these markets. This project represents a highly successful example of the potential for cost reduction in PEM electrolysis, and provides the initial stack design and manufacturing development for Proton’s MW scale product launch. The majority of the program focused on the bipolar assembly, from electrochemical modeling to subscale stack development through prototyping and manufacturing qualification for a large active area cell platform. Feasibility for an advanced membrane electrode assembly (MEA) with 50% reduction in catalyst loading was also demonstrated. Based on the progress in this program and other parallel efforts, H2A analysis shows the status of PEM electrolysis technology dropping below $3.50/kg production costs, exceeding the 2015 target.

  17. Evidence of catalytic production of hot hydrogen in rf generated hydrogen/argon plasmas

    CERN Document Server

    Phillips, J; Akhtar, K; Dhandapani, B; Mills, R; Phillips, Jonathan; Chen, Chun-Ku; Akhtar, Kamran; Dhandapani, Bala; Mills, Randell

    2005-01-01

    In this paper the selective broadening of the atomic hydrogen lines in pure H2 and Ar/H2 mixtures in a large 'GEC' cell (36 cm length_ 14 cm ID) was mapped as a function of position, H2/Ar ratio, time, power, and pressure. Several observations regarding the selective line broadening were particularly notable as they are unanticipated on the basis of earlier models. First, the anomalous broadening of the Balmer lines was found to exist throughout the plasma, and not just in the region between the electrodes. Second, the broadening was consistently a complex function of the operating parameters particularly gas composition (highest in pure H2), position, power, time and pressure. Clearly not anticipated by earlier models were the findings that under some conditions the highest concentration of 'hot' (>10 eV) hydrogen was found at the entry end, and not in the high field region between the electrodes and that in other conditions, the hottest H was at the (exit) pump (also grounded electrode) end. Third, excitati...

  18. Cobalt-Nanocrystal-Assembled Hollow Nanoparticles for Electrocatalytic Hydrogen Generation from Neutral-pH Water.

    Science.gov (United States)

    Liu, Bingrui; Zhang, Lin; Xiong, Weilin; Ma, Mingming

    2016-06-01

    Highly active and stable electrocatalysts for hydrogen generation from neutral-pH water are highly desired, but very difficult to achieve. Herein we report a facile synthetic approach to cobalt nanocrystal assembled hollow nanoparticles (Co-HNP), which serve as an electrocatalyst for hydrogen generation from neutral-pH water. An electrode composed of Co-HNP on a carbon cloth (CC) produces cathodic current densities of 10 and 100 mA cm(-2) at overpotentials of -85 mV and -237 mV, respectively. The Co-HNP/CC electrode retains its high activity after 20 h hydrogen generation at a high current density of 150 mA cm(-2) , indicating the superior activity and stability of Co-HNP as electrocatalyst. PMID:27125576

  19. Stabilization of Wind Energy Conversion System with Hydrogen Generator by Using EDLC Energy Storage System

    Science.gov (United States)

    Shishido, Seiji; Takahashi, Rion; Murata, Toshiaki; Tamura, Junji; Sugimasa, Masatoshi; Komura, Akiyoshi; Futami, Motoo; Ichinose, Masaya; Ide, Kazumasa

    The spread of wind power generation is progressed hugely in recent years from a viewpoint of environmental problems including global warming. Though wind power is considered as a very prospective energy source, wind power fluctuation due to the random fluctuation of wind speed has still created some problems. Therefore, research has been performed how to smooth the wind power fluctuation. This paper proposes Energy Capacitor System (ECS) for the smoothing of wind power which consists of Electric Double-Layer Capacitor (EDLC) and power electronics devices and works as an electric power storage system. Moreover, hydrogen has received much attention in recent years from a viewpoint of exhaustion problem of fossil fuel. Therefore it is also proposed that a hydrogen generator is installed at the wind farm to generate hydrogen. In this paper, the effectiveness of the proposed system is verified by the simulation analyses using PSCAD/EMTDC.

  20. Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in China

    Institute of Scientific and Technical Information of China (English)

    SHEN Ping; WANG Xiaofeng; XU Yin; SHI Baoguang; XU Yongchang

    2009-01-01

    The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals:δDCH4>-200‰,-250‰<δDCH4<-200‰ and δDCH4<-250‰. The forerunners believed that the main generation pathway of biogenic gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO2- reduction, the biogenic gas has heavy hydrogen isotopic composition: its δDCH4 values are higher than -200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: -250‰<δDCH4<-200‰, the δDCH4 values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO2- reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δDCH4<-250‰, and relatively heavy carbon isotopic

  1. Optimal generation scheduling for renewable microgrids using hydrogen storage systems

    OpenAIRE

    Petrollese, Mario

    2015-01-01

    The topic of this thesis is the development of a tool for an optimal energy management strategy (EMS) of the generators and energy storage systems constituent microgrids, both grid-connected or isolated (stand-alone power system) powered by Renewable Energy Sources (RES). In particular, a novel control system is designed based on the resolution of the unit commitment problem. For each time step, the proposed control system compares the expected power produced by the renewabl...

  2. Application of STATCOM/BESS for wind power smoothening and hydrogen generation

    Energy Technology Data Exchange (ETDEWEB)

    Muyeen, S.M.; Takahashi, Rion; Murata, Toshiaki; Tamura, Junji [Department of EEE, Kitami Institute of Technology, 165 Koen-cho, Hokkaido, Kitami 090-8507 (Japan); Ali, Mohd. Hasan [Department of Electrical and Computer Engineering, Ryerson University, 245 Church Street, Toronto (Canada)

    2009-02-15

    This paper proposes static synchronous compensator (STATCOM) incorporated with battery energy storage system (STATCOM/BESS) to smooth the line power of wind farm consists of fixed-speed wind generators. Constant output power reference is not a good choice because there may be some cases where wind speed is very low and then sufficient power cannot be obtained. In that case, energy storage device can solve the problem but large energy capacity may be needed. This paper proposes exponential moving average (EMA) to generate the reference output power, and thus the energy capacity of BESS unit can be small. Another salient feature of this study is the generation of hydrogen by using wind energy. At the wind farm terminal, two topologies of hydrogen generators are considered to be connected and their merits and demerits are analyzed. Finally, by taking the advantage of STATCOM/BESS, simple hydrogen generator topology composed of rectifier and electrolyzer is proposed. Detailed modeling and control strategy of hydrogen generator and STATCOM/BESS topologies are discussed and a cooperative control is developed. The effectiveness of the proposed system is verified by the simulation analysis using PSCAD/EMTDC. (author)

  3. Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyltetrazolate Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Luísa Martins

    2015-10-01

    Full Text Available Microwave assisted synthesis of the Cu(I compound [Cu(µ4-4-ptz]n [1, 4-ptz = 5-(4-pyridyltetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II compounds [Cu3(µ3-4-ptz4(µ2-N32(DMF2]n∙(DMF2n (2 and [Cu(µ2-4-ptz2(H2O2]n (3 using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane with aqueous hydrogen peroxide, under very mild conditions (at room temperature, without any added solvent or additive. The most efficient system (2/H2O2 showed, for the oxidation of cyclohexane, a turnover number (TON of 396 (TOF of 40 h−1, with an overall product yield (cyclohexanol and cyclohexanone of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 1–3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

  4. Development status of solid polymer electrolyte water electrolysis for large scale hydrogen generation

    Science.gov (United States)

    Russell, J. H.

    1981-03-01

    Solid polymer water electrolysis technology for large scale hydrogen generation is reviewed. A hydrogen generator module, capable of producing 2000 SCFH, was operated successfully for over 700 hours in the 200 kW system. Test results and further information are presented. Technology development was continued in support of improving both capital cost and conversion efficiency. Progress made in the development of the 10 sq ft active area cell included completion of the initial design, the beginning of fabrication development, and installation of new facilities for cell manufacture.

  5. Generating hydrogen for mobile devices; Wasserstofferzeugung fuer die mobile Anwendung

    Energy Technology Data Exchange (ETDEWEB)

    Schuetz, W. [Vodafone Pilotentwicklung GmbH, Muenchen (Germany)

    2001-10-01

    In future vehicles, more and more functions will be powered by electricity. These are for example ''steer by wire'', ''break by wire'', air conditioning and infotainment. This growing demand for electricity is a new challenge for the automotive industry. The so called APU (auxilliary power unit) is a convincing solution. This power generating unit based on fuel cell technology will provide electrical power in all operation situations. The article deals with the main focus of P{sup 21}-power for the 21st century, the Mannesmann Fuel Cell Product Center of the Vodafone Pilotentwicklung. (orig.)

  6. Photochemical hydrogen production from water catalyzed by CdTe quantum dots/molecular cobalt catalyst hybrid systems.

    Science.gov (United States)

    Han, Kai; Wang, Mei; Zhang, Shuai; Wu, Suli; Yang, Yong; Sun, Licheng

    2015-04-25

    A hybrid system with a coordinative interaction between a cobalt complex of a N2S2-tetradentate ligand and CdTe quantum dots displayed a high activity (initial TOF 850 h(-1)) and improved stability (TON 1.44 × 10(4) based on catalyst over 30 h) for the photochemical H2 generation from water, with a quantum efficiency of 5.32% at 400 nm. PMID:25800286

  7. Selective hydrogenation of 2-methyl-3-butyn-2-ol catalyzed by embedded polymer-protected PdZn nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Okhlopkova, Lyudmila B., E-mail: mila65@catalysis.ru; Matus, Ekaterina V.; Prosvirin, Igor P.; Kerzhentsev, Michail A.; Ismagilov, Zinfer R. [Boreskov Institute of Catalysis (Russian Federation)

    2015-12-15

    PdZn/TiO{sub 2} catalysts were synthesized by sol–gel method using a template Pluronic F127. PdZn nanoparticles with the size ranging from 1.7 to 2 nm were prepared by ethylene glycol reduction of ZnCl{sub 2} and Pd(CH{sub 3}COO){sub 2} in the presence of stabilizer and introduced into the matrix by addition into TiO{sub 2} sol, followed by different activation procedures. The structure, particles size, and chemical composition of nanoparticles and catalysts were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray fluorescence spectroscopy, and energy dispersive spectroscopy. The prepared catalysts have been tested in the selective hydrogenation of 2-methyl-3-butyn-2-ol, and the results have been compared with catalysts prepared by conventional impregnation. The results indicate that bimetallic PdZn nanoparticles-based catalysts show higher selectivity than corresponding monometallic Pd/TiO{sub 2}. Embedded on titania, bimetallic nanoparticles stabilized with polyvinylpyrrolidone exhibit good activity (1.1–1.8 mol MBY/mol Pd/s{sup −1}) and high selectivity to 2-methyl-3-buten-2-ol (81.5–88.9 % at 95 % conversion). The influence of the nature of the stabilizer, the stabilizer/metal molar ratio, and activation conditions on the catalytic behavior of the samples was analyzed. It is shown that the particle size does not significantly affect the catalytic properties in the range of 4.4–6.5 nm. The nature and amount of stabilizer seem to be crucial to prepare efficient catalyst.

  8. Hydrogen generation in microbial reverse-electrodialysis electrolysis cells using a heat-regenerated salt solution.

    Science.gov (United States)

    Nam, Joo-Youn; Cusick, Roland D; Kim, Younggy; Logan, Bruce E

    2012-05-01

    Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m(3) H(2)/m(3)·d, with a hydrogen yield of 3.4 mol H(2)/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes.

  9. Hydrogen Generation in Microbial Reverse-Electrodialysis Electrolysis Cells Using a Heat-Regenerated Salt Solution

    KAUST Repository

    Nam, Joo-Youn

    2012-05-01

    Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m3 H2/m3·d, with a hydrogen yield of 3.4 mol H2/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes. © 2012 American Chemical Society.

  10. Understanding oscillatory phenomena in molecular hydrogen generation via sodium borohydride hydrolysis.

    Science.gov (United States)

    Budroni, M A; Biosa, E; Garroni, S; Mulas, G R C; Marchettini, N; Culeddu, N; Rustici, M

    2013-11-14

    The hydrolysis of borohydride salts represents one of the most promising processes for the generation of high purity molecular hydrogen under mild conditions. In this work we show that the sodium borohydride hydrolysis exhibits a fingerprinting periodic oscillatory transient in the hydrogen flow over a wide range of experimental conditions. We disproved the possibility that flow oscillations are driven by supersaturation phenomena of gaseous bubbles in the reactive mixture or by a nonlinear thermal feedback according to a thermokinetic model. Our experimental results indicate that the NaBH4 hydrolysis is a spontaneous inorganic oscillator, in which the hydrogen flow oscillations are coupled to an "oscillophor" in the reactive solution. The discovery of this original oscillator paves the way for a new class of chemical oscillators, with fundamental implications not only for testing the general theory on oscillations, but also with a view to chemical control of borohydride systems used as a source of hydrogen based green fuel. PMID:24084866

  11. Coupling a PEM fuel cell and the hydrogen generation from aluminum waste cans

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Susana Silva; Albanil Sanchez, Loyda; Alvarez Gallegos, Alberto A. [Centro de Investigacion en Ingenieria y Ciencias Aplicadas, Av. Universidad 1001, Col. Chamilpa, Cuernavaca, Mor. CP 62210 (Mexico); Sebastian, P.J. [Centro de Investigacion en Energia-UNAM, 62580 Temixco, Morelos (Mexico); Cuerpo Academico de Energia y Sustentabilidad, UPCH, Tuxtla Gutierrez, Chiapas (Mexico)

    2007-10-15

    High purity hydrogen was generated from the chemical reaction of aluminum and sodium hydroxide. The aluminum used in this study was obtained from empty soft drink cans and treated with concentrated sulfuric acid to remove the paint and plastic film. One gram of aluminum was reacted with a solution of 2moldm{sup -3} of sodium hydroxide to produce hydrogen. The hydrogen produced from aluminum cans and oxygen obtained from a proton exchange membrane electrolyzer or air, was fed to a proton exchange membrane (PEM) fuel cell to produce electricity. Yields of 44 mmol of hydrogen contained in a volume of 1.760dm{sup 3} were produced from one gram of aluminum in a time period of 20 min. (author)

  12. Hydrogen-generating reactions in LWR severe accidents

    International Nuclear Information System (INIS)

    The available data on the reactions of Zircaloys, stainless steels, uranium metal and uranium dioxide with steam at temperatures above about 10000C and the reactions of core melts during concrete penetration have been reviewed and assessed for the IDCOR Program. The uranium metal is included because small quantities can be formed from the high temperature interaction between Zircaloy and uranium dioxide and because the uranium data adds insight into the nature of the reactions of core materials with steam. Thermodynamic analyses and comparisons of reaction rate data have been made. One of the purposes of this assessment was to develop fully the information generated in the early studies of oxidation processes, particularly the extensive program carried out at ANL from about 1960 to 1968

  13. Hydrogen generation in SRAT with nitric acid and late washing flowsheets

    International Nuclear Information System (INIS)

    Melter feed preparation processes, incorporating a final wash of the precipitate slurry feed to Defense Waste Processing Facility (DWPF) and a partial substitution of the SRAT formic acid requirement with nitric acid, should not produce peak hydrogen generation rates during Cold Chemical Runs (CCR's) and radioactive operation greater than their current, respective hydrogen design bases of 0.024 lb/hr and 1.5 lb/hr. A single SRAT bench-scale process simulation for CCR-s produced a DWPF equivalent peak hydrogen generation rate of 0.004 lb/hr. During radioactive operation, the peak hydrogen generation rate will be dependent on the extent DWPF deviates from the nominal precipitate hydrolysis and melter feed preparation process operating parameters. Two actual radioactive sludges were treated according to the new flowsheets. The peak hydrogen evolution rates were equivalent to 0.038 and 0.20 lb/hr (DWPF scale) respectively. Compared to the formic acid -- HAN hydrolysis flowsheets, these peak rates were reduced by a factor of 2.5 and 3.4 for Tank 15 and Tank 11 sludges, respectively

  14. WTP Waste Feed Qualification: Hydrogen Generation Rate Measurement Apparatus Testing Report

    Energy Technology Data Exchange (ETDEWEB)

    Stone, M. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Newell, J. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Smith, T. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Pareizs, J. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-06-01

    The generation rate of hydrogen gas in the Hanford tank waste will be measured during the qualification of the staged tank waste for processing in the Hanford Tank Waste Treatment and Immobilization Plant. Based on a review of past practices in measurement of the hydrogen generation, an apparatus to perform this measurement has been designed and tested for use during waste feed qualification. The hydrogen generation rate measurement apparatus described in this document and shown in Figure 0-1 utilized a 100 milliliter sample in a continuously-purged, continuously-stirred vessel, with measurement of hydrogen concentration in the vent gas. The vessel and lid had a combined 220 milliliters of headspace. The vent gas system included a small condenser to prevent excessive evaporative losses from the sample during the test, as well as a demister and filter to prevent particle migration from the sample to the gas chromatography system. The gas chromatograph was an on line automated instrument with a large-volume sample-injection system to allow measurement of very low hydrogen concentrations. This instrument automatically sampled the vent gas from the hydrogen generation rate measurement apparatus every five minutes and performed data regression in real time. The fabrication of the hydrogen generation rate measurement apparatus was in accordance with twenty three (23) design requirements documented in the conceptual design package, as well as seven (7) required developmental activities documented in the task plan associated with this work scope. The HGRMA was initially tested for proof of concept with physical simulants and a remote demonstration of the system was performed in the Savannah River National Laboratory Shielded Cells Mockup Facility. Final verification testing was performed using non-radioactive simulants of the Hanford tank waste. Three different simulants were tested to bound the expected rheological properties expected during waste feed qualification

  15. WTP Waste Feed Qualification: Hydrogen Generation Rate Measurement Apparatus Testing Report

    Energy Technology Data Exchange (ETDEWEB)

    Stone, M. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Newell, J. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Smith, T. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Pareizs, J. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-06-01

    The generation rate of hydrogen gas in the Hanford tank waste will be measured during the qualification of the staged tank waste for processing in the Hanford Tank Waste Treatment and Immobilization Plant. Based on a review of past practices in measurement of the hydrogen generation, an apparatus to perform this measurement has been designed and tested for use during waste feed qualification. The hydrogen generation rate measurement apparatus (HGRMA) described in this document utilized a 100 milliliter sample in a continuously-purged, continuously-stirred vessel, with measurement of hydrogen concentration in the vent gas. The vessel and lid had a combined 220 milliliters of headspace. The vent gas system included a small condenser to prevent excessive evaporative losses from the sample during the test, as well as a demister and filter to prevent particle migration from the sample to the gas chromatography system. The gas chromatograph was an on line automated instrument with a large-volume sample-injection system to allow measurement of very low hydrogen concentrations. This instrument automatically sampled the vent gas from the hydrogen generation rate measurement apparatus every five minutes and performed data regression in real time. The fabrication of the hydrogen generation rate measurement apparatus was in accordance with twenty three (23) design requirements documented in the conceptual design package, as well as seven (7) required developmental activities documented in the task plan associated with this work scope. The HGRMA was initially tested for proof of concept with physical simulants, and a remote demonstration of the system was performed in the Savannah River National Laboratory Shielded Cells Mockup Facility. Final verification testing was performed using non-radioactive simulants of the Hanford tank waste. Three different simulants were tested to bound the expected rheological properties expected during waste feed qualification testing. These

  16. Fuel processor and method for generating hydrogen for fuel cells

    Science.gov (United States)

    Ahmed, Shabbir; Lee, Sheldon H. D.; Carter, John David; Krumpelt, Michael; Myers, Deborah J.

    2009-07-21

    A method of producing a H.sub.2 rich gas stream includes supplying an O.sub.2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O.sub.2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent. The method still further includes contacting the cooled reformate stream with a catalyst that converts water and carbon monoxide to carbon dioxide and H.sub.2 in a water-gas-shift zone to produce a final reformate stream in the fuel processor.

  17. Start up system for hydrogen generator used with an internal combustion engine

    Science.gov (United States)

    Houseman, J.; Cerini, D. J. (Inventor)

    1977-01-01

    A hydrogen generator provides hydrogen rich product gases which are mixed with the fuel being supplied to an internal combustion engine for the purpose of enabling a very lean mixture of that fuel to be used, whereby nitrous oxides emitted by the engine are minimized. The hydrogen generator contains a catalyst which must be heated to a pre-determined temperature before it can react properly. To simplify the process of heating up the catalyst at start-up time, either some of the energy produced by the engine such as engine exhaust gas, or electrical energy produced by the engine, or the engine exhaust gas may be used to heat up air which is then used to heat the catalyst.

  18. Chemiluminescence assay for catechin based on generation of hydrogen peroxide in basic solution

    International Nuclear Information System (INIS)

    We have determined that the catechin group in basic solution efficiently produces hydrogen peroxide; moreover, a highly sensitive analysis methodology was developed to measure catechin employing a peroxalate chemiluminescence detection system. Identification of hydrogen peroxide generated by catechin was determined by ESR as well as peroxalate chemiluminescence using catalase and SOD. As a result, catechin-generated superoxide by electron reduction to dissolved oxygen in basic solution, followed by production of hydrogen peroxide through dismutation reaction. This method could measure several tea catechins, (+)-catechin (CC), (-)-epigallocatechin-3-gallate (EGCg), (-)-epicatechin-3-gallate (ECG) and gallic acid, with measurement range from 10-7 to 10-3 mol/l and sensitivity of 10-8 mol/l. This method was also applied to the determination of total catechin levels in green tea, black tea and roasted green tea

  19. Prostaglandins attenuate cardiac contractile dysfunction produced by free radical generation but not by hydrogen peroxide.

    Science.gov (United States)

    Zimmer, K M; Karmazyn, M

    1997-11-01

    The aim of this study was to examine and compare the potential influence of cyclooxygenase or lipoxygenase derived metabolites of arachidonic acid on myocardial injury produced either by a free radical generating system consisting of purine plus xanthine oxidase or that produced by hydrogen peroxide. A free radical generating system consisting of purine (2.3 mM) and xanthine oxidase (10 U/L) as well as hydrogen peroxide (75 microM) produced significant functional changes in the absence of either significant deficits in high energy phosphates or ultrastructural damage. Prostaglandin F2 alpha (30 nM) significantly attenuated both the negative inotropic effect of purine plus xanthine oxidase as well as the ability of the free radical generator to elevate diastolic pressure. An identical concentration of prostaglandin 12 (prostacyclin) significantly reduced diastolic pressure elevation only and had no effect on contractile depression. The salutary effects of the two PGs occurred in the absence of any inhibitory influence on superoxide anion generation produced by the purine and xanthine oxidase reaction. None of prostaglandins modulated the response to hydrogen peroxide. In addition, neither prostaglandin E2 nor leukotrienes exerted any effect on changes produced by either type of oxidative stress. A 5 fold elevation in the concentrations of free radical generators or hydrogen peroxide produced extensive injury as characterized by a virtual total loss in contractility, 400% elevation in diastolic pressure, ultrastructural damage and significant depletions in high energy phosphate content. None of these effects were modulated by eicosanoid treatment. Our results therefore demonstrate a selective ability of both prostaglandin F2 alpha and to a lesser extent prostacyclin, to attenuate dysfunction produced by purine plus xanthine oxidase but not hydrogen peroxide. It is possible that these eicosanoids may represent endogenous protective factors under conditions of enhanced

  20. Generation of Stoichiometric Ethylene and Isotopic Derivatives and Application in Transition Metal-Catalyzed Vinylation and Enyne Metathesis

    DEFF Research Database (Denmark)

    Min, Geanna; Bjerglund, Klaus Meier; Kramer, Søren;

    2013-01-01

    labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin....... This was demonstrated in the Ni-catalyzed Heck reaction with aryl triflates and benzyl chlorides, as well as Ru-mediated enyne metathesis....

  1. High Efficiency Generation of Hydrogen Fuels using Nuclear Power Annual Report August, 2000 - July 2001

    Energy Technology Data Exchange (ETDEWEB)

    Brown, L.C.

    2002-11-01

    OAK B188 High Efficiency Generation of Hydrogen Fuels using Nuclear Power Annual Report August 2000 - July 2001. Currently no large scale, cost-effective, environmentally attractive hydrogen production process is available for commercialization nor has such a process been identified. Hydrogen is a promising energy carrier, which potentially could replace the fossil fuels used in the transportation sector of our economy. Carbon dioxide emissions from fossil fuel combustion are thought to be responsible for global warming. The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high temperature heat from an advanced nuclear power station. The benefits of this work will include the generation of a low-polluting transportable energy feedstock in an efficient method that has little or no implication for greenhouse gas emissions from a primary energy source whose availability and sources are domestically controlled. This will help to ensure energy for a future transportation/energy infrastructure that is not influenced/controlled by foreign governments. This report describes work accomplished during the second year (Phase 2) of a three year project whose objective is to ''define an economically feasible concept for production of hydrogen, by nuclear means, using an advanced high temperature nuclear reactor as the energy source.'' The emphasis of the first year (Phase 1) was to evaluate thermochemical processes which offer the potential for efficient, cost-effective, large-scale production of hydrogen from water, in which the primary energy input is high temperature heat from an advanced nuclear reactor and to select one (or, at most, three) for further detailed consideration. Phase 1 met its goals and did select one process, the sulfur-iodine process, for investigation in Phases 2 and 3. The combined goals of Phases 2 and 3 were to select the advanced nuclear reactor best

  2. Modeling the reaction kinetics of a hydrogen generator onboard a fuel cell -- Electric hybrid motorcycle

    Science.gov (United States)

    Ganesh, Karthik

    Owing to the perceived decline of the fossil fuel reserves in the world and environmental issues like pollution, conventional fuels may be replaced by cleaner alternative fuels. The potential of hydrogen as a fuel in vehicular applications is being explored. Hydrogen as an energy carrier potentially finds applications in internal combustion engines and fuel cells because it is considered a clean fuel and has high specific energy. However, at 6 to 8 per kilogram, not only is hydrogen produced from conventional methods like steam reforming expensive, but also there are storage and handling issues, safety concerns and lack of hydrogen refilling stations across the country. The purpose of this research is to suggest a cheap and viable system that generates hydrogen on demand through a chemical reaction between an aluminum-water slurry and an aqueous sodium hydroxide solution to power a 2 kW fuel cell on a fuel cell hybrid motorcycle. This reaction is essentially an aluminum-water reaction where sodium hydroxide acts as a reaction promoter or catalyst. The Horizon 2000 fuel cell used for this purpose has a maximum hydrogen intake rate of 28 lpm. The study focuses on studying the exothermic reaction between the reactants and proposes a rate law that best describes the rate of generation of hydrogen in connection to the surface area of aluminum available for the certain reaction and the concentration of the sodium hydroxide solution. Further, the proposed rate law is used in the simulation model of the chemical reactor onboard the hybrid motorcycle to determine the hydrogen flow rate to the fuel cell with time. Based on the simulated rate of production of hydrogen from the chemical system, its feasibility of use on different drive cycles is analyzed. The rate of production of hydrogen with a higher concentration of sodium hydroxide and smaller aluminum powder size was found to enable the installation of the chemical reactor on urban cycles with frequent stops and starts

  3. High performance photoelectrochemical hydrogen generation and solar cells with a double type II heterojunction

    NARCIS (Netherlands)

    Lai, Lai-Hung; Gomulya, Widianta; Protesescu, Loredana; Kovalenko, Maksym V.; Loi, Maria A.

    2014-01-01

    We report on the fabrication of CdSe quantum dot (QD) sensitized electrodes by direct adsorption of colloidal QDs on mesoporous TiO2 followed by 3-mercaptopropionic acid (MPA) ligand exchange. High efficiency photoelectrochemical hydrogen generation is demonstrated by means of these electrodes. The

  4. Hydrogen generation by water radiolysis with immersion of oxidation products of Zircaloy-4

    International Nuclear Information System (INIS)

    In order to predict the hydrogen gas generation from seawater or water in which debris would be included by the severe accident of nuclear power plant, we investigated the effect of ZrO2 and the oxidation products of Zircaloy-4 on hydrogen gas generation by radiolysis of water since the radiolytic generation could be affected by materials immersed in water. Powders of well-characterized oxides and oxidation products were immersed in either seawater or distilled water, and irradiated by gamma ray from a Co-60 source. The observed hydrogen yield, G(H2), was measured as a function of the weight fraction of oxide in water up to 50 wt%. The enhancement of the hydrogen generation by radiolysis of water with the commercial oxides and the oxidation products of Zircaloy-4 was quite small or absent in seawater. But the enhancement was observed in the presence of the oxides or the oxidation products at low weight fraction in distilled water. This enhancement in distilled water seemed to be dependent on specific surface area or particle size, but its dependence on the crystal structure was not apparent in the experimental results. The enhancement was saturated at higher ZrO2 weight fractions and it was not apparent in the seawater. (author)

  5. The Effects of CO2 Addition on the Partial Oxidation of Heptane for Hydrogen Generation

    Institute of Scientific and Technical Information of China (English)

    Ran RAN; Guo Xing XIONG; Shi Shan SHENG; Wei Shen YANG

    2004-01-01

    The effects of CO2 on the partial oxidation of heptane for hydrogen generation have been studied. Based on the experimental results and thermodynamic equilibrium calculations, the validity of CO2 addition to weaken the hot spots, and the feasibility of the autothermal operation are discussed.

  6. Status of the development of solid polymer electrolyte water electrolysis for large scale hydrogen generation

    Science.gov (United States)

    Russell, J. H.

    1982-02-01

    Solid polymer electrolyte water electrolysis for large scale hydrogen generation is reported. The program was aimed at performance improvement. Reductions in cell impedance were demonstrated which improve cell performance by over 100 mV. A prototype 500 SCFH system for field evaluation was developed.

  7. Early-time photodynamics of ruthenium-based photocatalysts for light-induced hydrogen generation

    NARCIS (Netherlands)

    Pan, Qing

    2016-01-01

    This thesis aims to provide a fundamental understanding of the early-time photodynamics of a series of Ru/M (M = Pd or Pt) bimetallic photocatalysts for light-induced hydrogen generation. This class of complexes adopts a general structure involving a Ru(II) center coordinated to two peripheral ligan

  8. Biomass & Natural Gas Based Hydrogen Fuel For Gas Turbine (Power Generation)

    Science.gov (United States)

    Significant progress has been made by major power generation equipment manufacturers in the development of market applications for hydrogen fuel use in gas turbines in recent years. Development of a new application using gas turbines for significant reduction of power plant CO2 e...

  9. HIGH EFFICIENCY GENERATION OF HYDROGEN FUELS USING NUCLEAR POWER FINAL RECHNICAL REPORT FOR THE PERIOD AUGUST 1, 1999 THROUGH SEPTEMBER 30, 2002 REV. 1

    Energy Technology Data Exchange (ETDEWEB)

    BROWN,LC; BESENBRUCH,GE; LENTSCH, RD; SCHULTZ,KR; FUNK,JF; PICKARD,PS; MARSHALL,AC; SHOWALTER,SK

    2003-12-01

    carbon monoxide) that are detrimental to precious metal catalyzed fuel cells, as is now recognized by many of the world's largest automobile companies. Thermochemical hydrogen will not contain carbon monoxide as an impurity at any level. Electrolysis, the alternative process for producing hydrogen using nuclear energy, suffers from thermodynamic inefficiencies in both the production of electricity and in electrolytic parts of the process. The efficiency of electrolysis (electricity to hydrogen) is currently about 80%. Electric power generation efficiency would have to exceed 65% (thermal to electrical) for the combined efficiency to exceed the 52% (thermal to hydrogen) calculated for one thermochemical cycle. Thermochemical water-splitting cycles have been studied, at various levels of effort, for the past 35 years. They were extensively studied in the late 70s and early 80s but have received little attention in the past 10 years, particularly in the U.S. While there is no question about the technical feasibility and the potential for high efficiency, cycles with proven low cost and high efficiency have yet to be developed commercially. Over 100 cycles have been proposed, but substantial research has been executed on only a few. This report describes work accomplished during a three-year project whose objective is to ''define an economically feasible concept for production of hydrogen, by nuclear means, using an advanced high temperature nuclear reactor as the energy source.''

  10. A third-generation dispersion and third-generation hydrogen bonding corrected PM6 method

    DEFF Research Database (Denmark)

    Kromann, Jimmy Charnley; Christensen, Anders Steen; Svendsen, Casper Steinmann;

    2014-01-01

    We present new dispersion and hydrogen bond corrections to the PM6 method, PM6-D3H+, and its implementation in the GAMESS program. The method combines the DFT-D3 dispersion correction by Grimme et al. with a modified version of the H+ hydrogen bond correction by Korth. Overall, the interaction en...... vibrational free energies. While the GAMESS implementation is up to 10 times slower for geometry optimizations of proteins in bulk solvent, compared to MOPAC, it is sufficiently fast to make geometry optimizations of small proteins practically feasible....... energy of PM6-D3H+ is very similar to PM6-DH2 and PM6-DH+, with RMSD and MAD values within 0.02 kcal/mol of one another. The main difference is that the geometry optimizations of 88 complexes result in 82, 6, 0, and 0 geometries with 0, 1, 2, and 3 or more imaginary frequencies using PM6-D3H+ implemented...

  11. Evaluation of the pressure loads generated by hydrogen explosion in auxiliary nuclear building

    International Nuclear Information System (INIS)

    Full text of publication follows: In the framework of nuclear safety, a hydrogen leaks in the auxiliary nuclear building would raise a explosion hazard. A local ignition of the combustible mixture would give birth initially to a slow flame, rapidly accelerated by obstacles. This flame acceleration is responsible for high pressure loads that can damage the auxiliary building and destroy safety equipments in it. In this paper, we evaluate the pressure loads generated by an hydrogen explosion for both bounding and realistic explosion scenarios. The bounding scenarios use stoichiometric hydrogen-air mixtures and the realistic scenarios correspond to hydrogen leaks with mass flow rate varying between 1 g/s and 9 g/s. For every scenario, the impact of the ignition location and ignition time are investigated. The hydrogen dispersion and explosion are computed using the TONUS code. The dispersion model used is based on a finite element solver and the explosion is simulated by a structured finite volumes EULER equation solver and the combustion model CREBCOM which simulates the hydrogen/air turbulent flame propagation, taking into account 3D complex geometry and reactants concentration gradients. The pressure loads computed are then used to investigate the occurrence of a mechanical failure of the tanks located in the auxiliary nuclear building and containing radioactive fluids. The EUROPLEXUS code is used to perform 3D mechanical calculations because the loads are non uniform and of rather short deviation. (authors)

  12. A polymer electrolyte fuel cell stack for stationary power generation from hydrogen fuel

    Energy Technology Data Exchange (ETDEWEB)

    Gottesfeld, S. [Los Alamos National Lab., NM (United States)

    1995-09-01

    The fuel cell is the most efficient device for the conversion of hydrogen fuel to electric power. As such, the fuel cell represents a key element in efforts to demonstrate and implement hydrogen fuel utilization for electric power generation. The low temperature, polymer electrolyte membrane fuel cell (PEMFC) has recently been identified as an attractive option for stationary power generation, based on the relatively simple and benign materials employed, the zero-emission character of the device, and the expected high power density, high reliability and low cost. However, a PEMFC stack fueled by hydrogen with the combined properties of low cost, high performance and high reliability has not yet been demonstrated. Demonstration of such a stack will remove a significant barrier to implementation of this advanced technology for electric power generation from hydrogen. Work done in the past at LANL on the development of components and materials, particularly on advanced membrane/electrode assemblies (MEAs), has contributed significantly to the capability to demonstrate in the foreseeable future a PEMFC stack with the combined characteristics described above. A joint effort between LANL and an industrial stack manufacturer will result in the demonstration of such a fuel cell stack for stationary power generation. The stack could operate on hydrogen fuel derived from either natural gas or from renewable sources. The technical plan includes collaboration with a stack manufacturer (CRADA). It stresses the special requirements from a PEMFC in stationary power generation, particularly maximization of the energy conversion efficiency, extension of useful life to the 10 hours time scale and tolerance to impurities from the reforming of natural gas.

  13. Implementation of flowsheet change to minimize hydrogen and ammonia generation during chemical processing of high level waste in the defense waste processing facility

    Energy Technology Data Exchange (ETDEWEB)

    Lambert, Dan P. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Woodham, Wesley H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Williams, Matthew S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Newell, J. David [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Luther, Michelle C. [Auburn Univ., AL (United States); Brandenburg, Clayton H. [Univ.of South Carolina, Columbia, SC (United States)

    2016-09-27

    Testing was completed to develop a chemical processing flowsheet for the Defense Waste Processing Facility (DWPF), designed to vitrify and stabilize high level radioactive waste. DWPF processing uses a reducing acid (formic acid) and an oxidizing acid (nitric acid) to rheologically thin the slurry and complete the necessary acid base and reduction reactions (primarily mercury and manganese). Formic acid reduces mercuric oxide to elemental mercury, allowing the mercury to be removed during the boiling phase of processing through steam stripping. In runs with active catalysts, formic acid can decompose to hydrogen and nitrate can be reduced to ammonia, both flammable gases, due to rhodium and ruthenium catalysis. Replacement of formic acid with glycolic acid eliminates the generation of rhodium- and ruthenium-catalyzed hydrogen and ammonia. In addition, mercury reduction is still effective with glycolic acid. Hydrogen, ammonia and mercury are discussed in the body of the report. Ten abbreviated tests were completed to develop the operating window for implementation of the flowsheet and determine the impact of changes in acid stoichiometry and the blend of nitric and glycolic acid as it impacts various processing variables over a wide processing region. Three full-length 4-L lab-scale simulations demonstrated the viability of the flowsheet under planned operating conditions. The flowsheet is planned for implementation in early 2017.

  14. NOBLE METAL CHEMISTRY AND HYDROGEN GENERATION DURING SIMULATED DWPF MELTER FEED PREPARATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-06-25

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell vessels were performed with the primary purpose of producing melter feeds for the beaded frit program plus obtaining samples of simulated slurries containing high concentrations of noble metals for off-site analytical studies for the hydrogen program. Eight pairs of 22-L simulations were performed of the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles. These sixteen simulations did not contain mercury. Six pairs were trimmed with a single noble metal (Ag, Pd, Rh, or Ru). One pair had all four noble metals, and one pair had no noble metals. One supporting 4-L simulation was completed with Ru and Hg. Several other 4-L supporting tests with mercury have not yet been performed. This report covers the calculations performed on SRNL analytical and process data related to the noble metals and hydrogen generation. It was originally envisioned as a supporting document for the off-site analytical studies. Significant new findings were made, and many previous hypotheses and findings were given additional support as summarized below. The timing of hydrogen generation events was reproduced very well within each of the eight pairs of runs, e.g. the onset of hydrogen, peak in hydrogen, etc. occurred at nearly identical times. Peak generation rates and total SRAT masses of CO{sub 2} and oxides of nitrogen were reproduced well. Comparable measures for hydrogen were reproduced with more variability, but still reasonably well. The extent of the reproducibility of the results validates the conclusions that were drawn from the data.

  15. Estudio cinético de la descomposición catalizada de peróxido de hidrógeno sobre carbón activado Kinetic study of the catalyzed decomposition of hydrogen peroxide on activated carbon

    Directory of Open Access Journals (Sweden)

    Elihu Paternina

    2009-01-01

    Full Text Available The kinetic study of decomposition of hydrogen peroxide catalyzed by activated carbon was carried out. The effect of concentrations of reactants and temperature were experimentally studied. Kinetic data were evaluated using differential method of initial rates of reaction. When a typical kinetic law for reactions in homogeneous phase is used, first order of reaction is obtained for hydrogen peroxide and activated carbon, and activation energy of 27 kJ mol-1 for the reaction was estimated. Experimentally was observed that surface of activated carbon is chemically modified during decomposition of hydrogen peroxide, based on this result a scheme of reaction was proposed and evaluated. Experimental data fits very well to a Langmuir- Hinshelwood kinetic model and activation energy of 40 kJ mol-1 was estimated for reaction in heterogeneous phase.

  16. Comparative study of the hydrogen generation during short term station blackout (STSBO) in a BWR

    International Nuclear Information System (INIS)

    Highlights: • Comparative study of generation in a simulated STSBO severe accident. • MELCOR and SCDAP/RELAP5 codes were used to understanding the main phenomena. • Both codes present similar thermal-hydraulic behavior for pressure and boil off. • SCDAP/RELAP5 predicts 15.8% lower hydrogen production than MELCOR. - Abstract: The aim of this work is the comparative study of hydrogen generation and the associated parameters in a simulated severe accident of a short-term station blackout (STSBO) in a typical BWR-5 with Mark-II containment. MELCOR (v.1.8.6) and SCDAP/RELAP5 (Mod.3.4) codes were used to understand the main phenomena in the STSBO event through the results comparison obtained from simulations with these codes. Due that the simulation scope of SCDAP/RELAP5 is limited to failure of the vessel pressure boundary, the comparison was focused on in-vessel severe accident phenomena; with a special interest in the vessel pressure, boil of cooling, core temperature, and hydrogen generation. The results show that at the beginning of the scenario, both codes present similar thermal-hydraulic behavior for pressure and boil off of cooling, but during the relocation, the pressure and boil off, present differences in timing and order of magnitude. Both codes predict in similar time the beginning of melting material drop to the lower head. As far as the hydrogen production rate, SCDAP/RELAP5 predicts 15.8% lower production than MELCOR

  17. Brewery wastewaters in photobiological hydrogen generation in presence of Rhodobacter sphaeroides O.U. 001

    Energy Technology Data Exchange (ETDEWEB)

    Seifert, K.; Waligorska, M.; Laniecki, M. [Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznan (Poland)

    2010-05-15

    Rhodobacter sphaeroides O.U. 001 (concentration of inoculum-0.36 g dry wt/l) and brewery wastewaters were applied in photobiogeneration of hydrogen under illumination of 116 W/m{sup 2}. The best results were obtained with filtered wastewaters sterilized at 120 C for 20 min and maximal concentration of waste in medium equal 10% v/v. The main product in generated biogas was hydrogen (90%). After sterilization the amount of generated hydrogen was tripled (from 0.76 to 2.2 l H{sub 2}/l medium), whereas waste concentration of 10% v/v resulted in the best substrate yield (0.22 l H{sub 2}/l of waste). Under these conditions the amount of generated hydrogen was 2.24 l H{sub 2}/l medium and light conversion efficiency reached value of 1.7%. The modified Gompertz equations served in modeling of the kinetics of the studied process. (author)

  18. High Efficiency Generation of Hydrogen Fuels Using Solar Thermochemical Splitting of Water

    Energy Technology Data Exchange (ETDEWEB)

    Heske, Clemens; Moujaes, Samir; Weimer, Alan; Wong, Bunsen; Siegal, Nathan; McFarland, Eric; Miller, Eric; Lewis, Michele; Bingham, Carl; Roth, Kurth; Sabacky, Bruce; Steinfeld, Aldo

    2011-09-29

    The objective of this work is to identify economically feasible concepts for the production of hydrogen from water using solar energy. The ultimate project objective was to select one or more competitive concepts for pilot-scale demonstration using concentrated solar energy. Results of pilot scale plant performance would be used as foundation for seeking public and private resources for full-scale plant development and testing. Economical success in this venture would afford the public with a renewable and limitless source of energy carrier for use in electric power load-leveling and as a carbon-free transportation fuel. The Solar Hydrogen Generation Research (SHGR) project embraces technologies relevant to hydrogen research under the Office of Hydrogen Fuel Cells and Infrastructure Technology (HFCIT) as well as concentrated solar power under the Office of Solar Energy Technologies (SET). Although the photoelectrochemical work is aligned with HFCIT, some of the technologies in this effort are also consistent with the skills and technologies found in concentrated solar power and photovoltaic technology under the Office of Solar Energy Technologies (SET). Hydrogen production by thermo-chemical water-splitting is a chemical process that accomplishes the decomposition of water into hydrogen and oxygen using only heat or a combination of heat and electrolysis instead of pure electrolysis and meets the goals for hydrogen production using only water and renewable solar energy as feed-stocks. Photoelectrochemical hydrogen production also meets these goals by implementing photo-electrolysis at the surface of a semiconductor in contact with an electrolyte with bias provided by a photovoltaic source. Here, water splitting is a photo-electrolytic process in which hydrogen is produced using only solar photons and water as feed-stocks. The thermochemical hydrogen task engendered formal collaborations among two universities, three national laboratories and two private sector

  19. Revaluation of hydrogen generation by water radiolysis in SDS vessels at TMI-2 accident

    International Nuclear Information System (INIS)

    Two years after Three Mile Island Unit 2 (TMI-2) loss-of-coolant accident, radioactive contaminated water has been processed by Submerged Demineralizer System (SDS) with two types of zeolite adsorbents to remove radioactive nuclides of Sr-90, Cs-134 and Cs-137. During and after the process, adsorption amount and distribution of nuclides on the zeolites, residual water content and thermal conductivity in the SDS vessels have been measured or estimated for verification of safety in the process, subsequent transportation and disposal. Hydrogen generation has been also evaluated mainly by direct monitoring in the large-scale of vessel after the process. In this work, the revaluation of hydrogen generation was demonstrated on the basis of the open information of vessel, and the latest experimental data obtained in adsorption and radiolysis occurring in small-scale of zeolite-water mixtures. As a property of the zeolites (UOP IE-96, A-51), adsorption and desorption of water vapour on the zeolites were observed as a function of relative pressure corresponding to relative humidity. 10-20 wt% of water was found to be physically and chemically adsorbed on the zeolites within normal humidity of 20 to 90 %RH, reflecting residual water content absorbed on the dominant zeolites in the dewatering of vessels after the process. Hydrogen generated in the radiolysis of zeolite-water mixtures was further measured to obtain the observed yields of hydrogen as functions of water content in the mixtures and of the height of mixtures. It was found that additional water radiolysis took place through the energy dissipation of radiation to the zeolites, and that liquid depth effect on the yield in water was depressed by adding zeolites to water. Based on these experimental results and further estimations, hydrogen generation dependent on decay heat and water content in the SDS vessel was finally revaluated. The procedure and results in this revaluation would be helpful for the decontamination

  20. End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Ronald Okoth

    2013-03-01

    Full Text Available Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I-catalyzed azide–alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.

  1. Interaction of gas phase atomic hydrogen with Pt(111): Direct evidence for the formation of bulk hydrogen species

    Institute of Scientific and Technical Information of China (English)

    JIANG ZhiQuan; HUANG WeiXin; BAO XinHe

    2007-01-01

    Employing hot tungsten filament to thermal dissociate molecular hydrogen, we generated gas phase atomic hydrogen under ultra-high vacuum (UHV) conditions and investigated its interaction with Pt(111) surface. Thermal desorption spectroscopy (TDS) results demonstrate that adsorption of molecular hydrogen on Pt(111) forms surface Had species whereas adsorption of atomic hydrogen forms not only surface Had species but also bulk Had species. Bulk Had species is more thermal-unstable than surface Had species on Pt(111), suggesting that bulk Had species is more energetic. This kind of weakly- adsorbed bulk Had species might be the active hydrogen species in the Pt-catalyzed hydrogenation reactions.

  2. SLUDGE BATCH 4 FOLLOW-UP QUALIFICATION STUDIES TO EVALUATE HYDROGEN GENERATION

    Energy Technology Data Exchange (ETDEWEB)

    Pareizs, J; David Koopman, D; Dan Lambert, D; Cj Bannochie, C

    2007-08-23

    Follow-up testing was conducted to better understand the excessive hydrogen generation seen in the initial Sludge Batch 4 (SB4) qualification Sludge Receipt and Adjustment Tank/Slurry Mix Evaporator (SRAT/SME) simulation in the Savannah River National Laboratory (SRNL) Shielded Cells. This effort included both radioactive and simulant work. The initial SB4 qualification test produced 0.59 lbs/hr hydrogen in the SRAT, which was just below the DWPF SRAT limit of 0.65 lbs/hr, and the test produced over 0.5 lbs/hr hydrogen in the SME cycle on two separate occasions, which were over the DWPF SME limit of 0.223 lbs/hr.

  3. Generation of tubular beams of negative hydrogen ions by a surface plasma source

    International Nuclear Information System (INIS)

    The results of experiments on obtaining a tubular beam of hydrogen negative ions from a surface plasma source with emission ring slit of 100 mm diameter are described in the study. Conditions of burning of a high current ring discharge generating effectively hydrogen negative ions with current density up to 2.1 A/cm2 are investigated. The possibility of generation of intensive tubular beams of hydrogen negative ions by surface plasma sources is shown, the 2.4 A ion beam is obtained. The results of preliminary experiments on accelerating tubular beam up to 135 keV are described. Azymuthally uniform current density distribution of intensive tubular beams generated by discharges with a close electron drift in a surface plasma source with emission ring slit, absence of high-frequency oscillations in optimal conditions of sources operation as well as the possibility of the most complete use of generated by the discharge negative ions flow show the prospects of development of these sources for fast atom injectors

  4. In situ generation of hydrogen from water by aluminum corrosion in solutions of sodium aluminate

    Energy Technology Data Exchange (ETDEWEB)

    Soler, Lluis; Candela, Angelica Maria; Munoz, Maria; Casado, Juan [Centre Grup de Tecniques de Separacio en Quimica (GTS), Unitat de Quimica Analitica, Departament de Quimica, Universitat Autonoma de Barcelona, Campus UAB s/n, 08193 Bellaterra, Barcelona, Catalonia (Spain); Macanas, Jorge [Laboratoire de Genie Chimique, UMR 5503 CNRS-INPT-UPS, Universite de Toulouse, Toulouse (France)

    2009-07-01

    A new process to obtain hydrogen from water using aluminum in sodium aluminate solutions is described and compared with results obtained in aqueous sodium hydroxide. This process consumes only water and aluminum, which are raw materials much cheaper than other compounds used for in situ hydrogen generation, such as hydrocarbons and chemical hydrides, respectively. As a consequence, our process could be an economically feasible alternative for hydrogen to supply fuel cells. Results showed an improvement of the maximum rates and yields of hydrogen production when NaAlO{sub 2} was used instead of NaOH in aqueous solutions. Yields of 100% have been reached using NaAlO{sub 2} concentrations higher than 0.65 M and first order kinetics at concentrations below 0.75 M has been confirmed. Two different heterogeneous kinetic models are verified for NaAlO{sub 2} aqueous solutions. The activation energy (E{sub a}) of the process with NaAlO{sub 2} is 71 kJ mol{sup -1}, confirming a control by a chemical step. A mechanism unifying the behavior of Al corrosion in NaOH and NaAlO{sub 2} solutions is presented. The application of this process could reduce costs in power sources based on fuel cells that nowadays use hydrides as raw material for hydrogen production. (author)

  5. A polymer electrolyte fuel cell stack for stationary power generation from hydrogen fuel

    Energy Technology Data Exchange (ETDEWEB)

    Zawodzinski, C.; Wilson, M.; Gottesfeld, S. [Los Alamos National Lab., NM (United States)

    1996-10-01

    The fuel cell is the most efficient device for the conversion of hydrogen fuel to electric power. As such, the fuel cell represents a key element in efforts to demonstrate and implement hydrogen fuel utilization for electric power generation. A central objective of a LANL/Industry collaborative effort supported by the Hydrogen Program is to integrate PEM fuel cell and novel stack designs at LANL with stack technology of H-Power Corporation (H-Power) in order to develop a manufacturable, low-cost/high-performance hydrogen/air fuel cell stack for stationary generation of electric power. A LANL/H-Power CRADA includes Tasks ranging from exchange, testing and optimization of membrane-electrode assemblies of large areas, development and demonstration of manufacturable flow field, backing and bipolar plate components, and testing of stacks at the 3-5 cell level and, finally, at the 4-5 kW level. The stack should demonstrate the basic features of manufacturability, overall low cost and high energy conversion efficiency. Plans for future work are to continue the CRADA work along the time line defined in a two-year program, to continue the LANL activities of developing and testing stainless steel hardware for longer term stability including testing in a stack, and to further enhance air cathode performance to achieve higher energy conversion efficiencies as required for stationary power application.

  6. Acetaldehyde behavior over platinum based catalyst in hydrogen stream generated by ethanol reforming

    Energy Technology Data Exchange (ETDEWEB)

    de Lima, Adriana F.F. [Laboratorio de Catalise, Instituto Nacional de Tecnologia, Av. Venezuela 82/507, 20081-310 Rio de Janeiro, RJ (Brazil); Instituto de Quimica e INOG (Instituto Nacional de Oleo Gas), UERJ-CNPq, FAPERJ, Universidade do Estado do Rio de Janeiro, Rua Sao Francisco Xavier, 524, 20550-900 Rio de Janeiro, RJ (Brazil); Colman, Rita C. [Departamento de Engenharia Quimica e de Petroleo, Universidade Federal Fluminense, Av. Passos da Patria, 156/bl E/240, 24210-240 Niteroi, RJ (Brazil); Zotin, Fatima M.Z. [Instituto de Quimica e INOG (Instituto Nacional de Oleo Gas), UERJ-CNPq, FAPERJ, Universidade do Estado do Rio de Janeiro, Rua Sao Francisco Xavier, 524, 20550-900 Rio de Janeiro, RJ (Brazil); CETEM-MCT, Av. Pedro Calmon, 900, Cidade Universitaria, 21941-908 Rio de Janeiro, RJ (Brazil); Appel, Lucia G. [Laboratorio de Catalise, Instituto Nacional de Tecnologia, Av. Venezuela 82/507, 20081-310 Rio de Janeiro, RJ (Brazil)

    2010-12-15

    Due to the greenhouse effect, hydrogen production from bioethanol reforming is a very important subject in heterogeneous catalysis research. Pt based catalysts are employed in H{sub 2} purification processes and also as electrocatalysts of PEM (''Proton Exchange Membrane'') fuel cells. Hydrogen obtained from ethanol reforming may contain, as contaminants, acetaldehyde and small amounts of CO. This aldehyde can be decarbonylated on Pt based catalysts generating carbon monoxide and methane, rendering the hydrogen purification more challenging. Moreover, acetaldehyde might also change the electrocatalyst behavior. Therefore, this contribution aims at studying the acetaldehyde behavior in the presence of platinum based catalysts in hydrogen atmosphere. The Pt/SiO{sub 2}, Pt/USY catalysts and an electrocatalyst were characterized by n-butylamine, H{sub 2} and CO{sub 2} adsorption, ATG/DTG measurements and cyclohexane dehydrogenation reaction. It was observed that the acid-basic properties of the supports promote condensation reactions. When in contact with Pt based catalysts, acetaldehyde undergoes C-C and C=O bond scissions. The former occurs at a wide range of temperatures, whereas the latter only at low temperatures (<200 C). The C-C bond scission (decarbonylation) produces methane and CO. The C=O bond scission generates carbon residues on the catalyst as well as oxygen species, which in turn is able to eliminate CO from the catalytic surface. The data also show that decarbonylation is not a structure-sensitive reaction. (author)

  7. Rapid hydrogen gas generation using reactive thermal decomposition of uranium hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Kanouff, Michael P.; Van Blarigan, Peter; Robinson, David B.; Shugard, Andrew D.; Gharagozloo, Patricia E.; Buffleben, George M.; James, Scott Carlton; Mills, Bernice E.

    2011-09-01

    Oxygen gas injection has been studied as one method for rapidly generating hydrogen gas from a uranium hydride storage system. Small scale reactors, 2.9 g UH{sub 3}, were used to study the process experimentally. Complimentary numerical simulations were used to better characterize and understand the strongly coupled chemical and thermal transport processes controlling hydrogen gas liberation. The results indicate that UH{sub 3} and O{sub 2} are sufficiently reactive to enable a well designed system to release gram quantities of hydrogen in {approx} 2 seconds over a broad temperature range. The major system-design challenge appears to be heat management. In addition to the oxidation tests, H/D isotope exchange experiments were performed. The rate limiting step in the overall gas-to-particle exchange process was found to be hydrogen diffusion in the {approx}0.5 {mu}m hydride particles. The experiments generated a set of high quality experimental data; from which effective intra-particle diffusion coefficients can be inferred.

  8. Research and development of foreign submarine sodium borohydride hydrolysis hydrogen generation%国外潜艇硼氢化钠水解制氢的研究与进展

    Institute of Scientific and Technical Information of China (English)

    李宏伟; 李大鹏; 张晓东

    2012-01-01

    叙述了国外潜艇AIP装置硼氢化钠水解制氢的研究与进展,介绍了硼氢化钠溶液水解制氢方法、水解反应催化剂,描述了潜艇硼氢化钠水解制氢系统、管式和一体式硼氢化钠水解制氢反应器的组成与工作,分析了制氢器反应区内的两相流动现象、反应区体积和换热-冷凝器传热面积要求,以及制氢器内液滴的分离、固体颗粒的沉淀和悬浮物的过滤、制氢器的动态特性等问题.%Research and development of foreign submarine AIP sodium borohydride hydrolysis hydrogen generation is stated in this paper. Method and catalyzer of sodium borohydride hydrolysis hydrogen generation are introduced. Submarine system of sodium borohydride hydrolysis hydrogen generation, constitution and working of tubular and integrative reactors of sodium borohydride hydrolysis hydrogen generation are described. Two-phase flow phenomena, requirements of reactor volume and heat-transfer surface of heat-exchanger-condenser, separation of liquid dribbles, precipitin of solid grains and filtration of suspending particles in the hydrogen generator, as well as dynamic characteristic of hydrogen generator are analyzed.

  9. Photo-driven autonomous hydrogen generation system based on hierarchically shelled ZnO nanostructures

    International Nuclear Information System (INIS)

    A quantum dot semiconductor sensitized hierarchically shelled one-dimensional ZnO nanostructure has been applied as a quasi-artificial leaf for hydrogen generation. The optimized ZnO nanostructure consists of one dimensional nanowire as a core and two-dimensional nanosheet on the nanowire surface. Furthermore, the quantum dot semiconductors deposited on the ZnO nanostructures provide visible light harvesting properties. To realize the artificial leaf, we applied the ZnO based nanostructure as a photoelectrode with non-wired Z-scheme system. The demonstrated un-assisted photoelectrochemical system showed the hydrogen generation properties under 1 sun condition irradiation. In addition, the quantum dot modified photoelectrode showed 2 mA/cm2 current density at the un-assisted condition

  10. Safety operation of chromatography column system with discharging hydrogen radiolytically generated

    Directory of Open Access Journals (Sweden)

    Watanabe Sou

    2015-01-01

    Full Text Available In the extraction chromatography system, accumulation of hydrogen gas in the chromatography column is suspected to lead to fire or explosion. In order to prevent the hazardous accidents, it is necessary to evaluate behaviors of gas radiolytically generated inside the column. In this study, behaviors of gas inside the extraction chromatography column were investigated through experiments and Computation Fluid Dynamics (CFD simulation. N2 gas once accumulated as bubbles in the packed bed was hardly discharged by the flow of mobile phase. However, the CFD simulation and X-ray imaging on γ-ray irradiated column revealed that during operation the hydrogen gas generated in the column was dissolved into the mobile phase without accumulation and discharged.

  11. Double-side illuminated titania nanotubes for high volume hydrogen generation by water splitting

    International Nuclear Information System (INIS)

    A sonoelectrochemical anodization method is proposed to synthesize TiO2 nanotubular arrays on both sides of a titanium foil (TiO2/Ti/TiO2). Highly ordered TiO2 nanotubular arrays of 16 cm2 area with uniform surface distribution can be obtained using this anodization procedure. These double-sided TiO2/Ti/TiO2 materials are used as both photoanode (carbon-doped titania nanotubes) and cathode (Pt nanoparticles dispersed on TiO2 nanotubes; PtTiO2/Ti/PtTiO2) in a specially designed photoelectrochemical cell to generate hydrogen by water splitting at a rate of 38 ml h-1. The nanomaterials are characterized by FESEM, HRTEM, STEM, EDS, FFT, SAED and XPS techniques. The present approach can be used for large-scale hydrogen generation using renewable energy sources

  12. Graphene sheets/cobalt nanocomposites as low-cost/high-performance catalysts for hydrogen generation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fei; Hou, Chengyi; Zhang, Qinghong [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); Wang, Hongzhi, E-mail: wanghz@dhu.edu.cn [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); Li, Yaogang, E-mail: yaogang_li@dhu.edu.cn [College of Materials Science and Engineering, Donghua University, Shanghai 201620 (China)

    2012-08-15

    The production of clean and renewable hydrogen through the hydrolysis of sodium borohydride has received much attention owing to increasing global energy demands. Graphene sheets/cobalt (GRs/Co) nanocomposites, which are highly efficient catalysts, have been prepared using a one-step solvothermal method in ethylene glycol. Co{sup 2+} salts were converted to Co nanoparticles, which were simultaneously inserted into the graphene layers with the reduction of graphite oxide sheets to GRs. The as-synthesized samples were characterized by X-ray diffraction, Fourier transform infrared spectra, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and vibrating sample magnetometer. The maximum saturation magnetization value reached 80.8 emu g{sup -1}, meaning they are more suitable for magnet-controlled generation of H{sub 2} than noble metal catalysts. The catalytic activity of the composite was investigated by the hydrolysis of sodium borohydride in aqueous solution both with and without a GRs support. It was found that the high electronic conductive GRs support increased the hydrogen generation rate (about two times) compared with pure cobalt. The improved hydrogen generation rate, low cost and uncomplicated recycling makes the GRs/Co nanocomposites promising candidates as catalysts for hydrogen generation. Highlights: Black-Right-Pointing-Pointer Graphene sheets/cobalt nanocomposites were prepared by a one-step solvothermal method. Black-Right-Pointing-Pointer The maximum saturation magnetization value of the composites reached 80.8 emu g{sup -1}. Black-Right-Pointing-Pointer The graphene support greatly increased the catalytic activity of cobalt. Black-Right-Pointing-Pointer An easily removed, recycled and controlled functional filter was obtained.

  13. Hydrogen generation by photoelectrochemical effect of the Cu-doped TiO2 photoanode

    International Nuclear Information System (INIS)

    TiO2 film photoanodes with a size of 1 × 1 cm2 were fabricated by a spin coating method. Cu-doped TiO2 powder with various Cu concentrations (0.2, 0.4, 0.6 and 0.8 at%) and surfactant were used as starting materials in coating Cu-doped TiO2 thin films onto FTO/glass substrate. Crystalline structure of TiO2 material, microstructure of the photoanode films and their thickness were identified by x-ray diffraction and Raman scattering. Hydrogen generation from water by photoelectrochemical effect in the visible light was observed by recording I/V characteristics of the photoanode in dark and light regimes. The obtained results have shown that the hydrogen generation efficiency of photoanode nonlinearly depends on Cu concentration. The nonlinear dependence of the hydrogen generation efficiency may be due to a change of resistivity of the film photoanode that is related with the random distribution of the hetero-junction between interfaces of TiO2 and CuO nanoparticles. (paper)

  14. Easy synthesis of bismuth iron oxide nanoparticles as photocatalyst for solar hydrogen generation from water

    Science.gov (United States)

    Deng, Jinyi

    In this study, high purity bismuth iron oxide (BiFeO3/BFO) nanoparticles of size 50-80 nm have been successfully synthesized by a simple sol-gel method using urea and polyvinyl alcohol at low temperature. X-ray diffraction (XRD) measurement is used to optimize the synthetic process to get highly crystalline and pure phase material. Diffuse reflectance ultraviolet-visible (DRUV-Vis) spectrum indicates that the absorption cut-off wavelength of the nanoparticles is about 620 nm, corresponding to an energy band gap of 2.1 eV. Compared to BaTiO3, BFO has a better degradation of methyl orange under light radiation. Also, photocatalytic tests prove this material to be efficient towards water splitting under simulated solar light to generate hydrogen. The simple synthetic methodology adopted in this paper will be useful in developing low-cost semiconductor materials as effective photocatalysts for hydrogen generation. Photocatalytic tests followed by gas chromatography (GC) analyses show that BiFeO3 generates three times more hydrogen than commercial titania P25 catalyst under the same experimental conditions.

  15. Mixed Ionic and Electonic Conductors for Hydrogen Generation and Separation: A New Approach

    Energy Technology Data Exchange (ETDEWEB)

    Srikanth Gopalan

    2006-12-31

    Composite mixed conductors comprising one electronic conducting phase, and one ionic conducting phase (MIECs) have been developed in this work. Such MIECs have applications in generating and separating hydrogen from hydrocarbon fuels at high process rates and high purities. The ionic conducting phase comprises of rare-earth doped ceria and the electronic conducting phase of rare-earth doped strontium titanate. These compositions are ideally suited for the hydrogen separation application. In the process studied in this project, steam at high temperatures is fed to one side of the MIEC membrane and hydrocarbon fuel or reformed hydrocarbon fuel to the other side of the membrane. Oxygen is transported from the steam side to the fuel side down the electrochemical potential gradient thereby enriching the steam side flow in hydrogen. The remnant water vapor can then be condensed to obtain high purity hydrogen. In this work we have shown that two-phase MIECs comprising rare-earth ceria as the ionic conductor and doped-strontium titanate as the electronic conductor are stable in the operating environment of the MIEC. Further, no adverse reaction products are formed when these phases are in contact at elevated temperatures. The composite MIECs have been characterized using a transient electrical conductivity relaxation technique to measure the oxygen chemical diffusivity and the surface exchange coefficient. Oxygen permeation and hydrogen generation rates have been measured under a range of process conditions and the results have been fit to a model which incorporates the oxygen chemical diffusivity and the surface exchange coefficient from the transient measurements.

  16. Hydrogen gas generation from refuse-derived fuel (RDF) under wet conditions.

    Science.gov (United States)

    Sakka, Makiko; Kimura, Tetsuya; Sakka, Kazuo; Ohmiya, Kunio

    2004-02-01

    An explosion has recently occurred at a silo containing refuse-derived fuels (RDF) in Japan. There is a possibility that microorganisms are involved in generation of combustible gas from RDF and this study was aimed at showing the presence of bacteria that can ferment RDF pellets. All RDF samples tested contained a relatively high number of viable bacterial cells, 1.4x10(5) to 3.2x10(6) viable cells/g. These bacteria in the RDF samples fermented them to generate heat and hydrogen gas. PMID:14981319

  17. Investigation of the high-order harmonic generation and ionization of model hydrogen atom and real hydrogen atom in intense laser field

    International Nuclear Information System (INIS)

    Solving time-dependent Schroedinger equation numerically, we investigate the high-order harmonic generation and ionization probability of one dimensional, two dimensional and three dimensional hydrogen atom exposed to intense laser field. In the tunneling ionization regime, our results show that the HHG plateau features and cutoff positions of model hydrogen atoms are well agreement with those of real hydrogen atom, and the trend of changing of the ionization probabilities with time is similar, but the values of ionization probabilities for model atoms are different from ones for three dimensional hydrogen atom. We explain the reason for the difference of ionization probabilities between model atoms and real hydrogen atom according to the semiclassical three-step model. (author)

  18. Multi-Generation Concentrating Solar-Hydrogen Power System for Sustainable Rural Development

    Energy Technology Data Exchange (ETDEWEB)

    Krothapalli, A.; Greska, B.

    2007-07-01

    This paper describes an energy system that is designed to meet the demands of rural populations that currently have no access to grid-connected electricity. Besides electricity, it is well recognized that rural populations need at least a centralized refrigeration system for storage of medicines and other emergency supplies, as well as safe drinking water. Here we propose a district system that will employ a multi-generation concentrated solar power (CSP) system that will generate electricity and supply the heat needed for both absorption refrigeration and membrane distillation (MD) water purification. The electricity will be used to generate hydrogen through highly efficient water electrolysis and individual households can use the hydrogen for generating electricity, via affordable proton exchange membrane (PEM) fuel cells, and as a fuel for cooking. The multi-generation system is being developed such that its components will be easy to manufacture and maintain. As a result, these components will be less efficient than their typical counterparts but their low cost-to-efficiency ratio will allow for us to meet our installation cost goal of $1/Watt for the entire system. The objective of this paper is to introduce the system concept and discuss the system components that are currently under development. (auth)

  19. The effect of plutonium dioxide water surface coverage on the generation of hydrogen and oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Veirs, Douglas K. [Los Alamos National Laboratory; Berg, John M. [Los Alamos National Laboratory; Crowder, Mark L. [Savannah River National Laboratory

    2012-06-20

    The conditions for the production of oxygen during radiolysis of water adsorbed onto plutonium dioxide powder are discussed. Studies in the literature investigating the radiolysis of water show that both oxygen and hydrogen can be generated from water adsorbed on high-purity plutonium dioxide powder. These studies indicate that there is a threshold in the amount of water below which oxygen is not generated. The threshold is associated with the number of monolayers of adsorbed water and is shown to occur at approximately two monolayers of molecularly adsorbed water. Material in equilibrium with 50% relative humidity (RH) will be at the threshold for oxygen generation. Using two monolayers of molecularly adsorbed water as the threshold for oxygen production, the total pressure under various conditions is calculated assuming stoichiometric production of hydrogen and oxygen. The specific surface area of the oxide has a strong effect on the final partial pressure. The specific surface areas resulting in the highest pressures within a 3013 container are evaluated. The potential for oxygen generation is mitigated by reduced relative humidity, and hence moisture adsorption, at the oxide surface which occurs if the oxide is warmer than the ambient air. The potential for oxygen generation approaches zero as the temperature difference between the ambient air and the material approaches 6 C.

  20. Broadband, stable and highly coherent supercontinuum generation at telecommunication wavelengths in an hydrogenated amorphous silicon waveguide

    CERN Document Server

    Leo, F; Kuyken, B; Roelkens, G; Gorza, S -P

    2014-01-01

    Hydrogenated amorphous silicon (a:Si-H) has recently been recognized as a highly nonlinear CMOS compatible photonic platform. We experimentally demonstrate the generation of a supercontinuum (SC) spanning over 500 nm in a-Si:H photonic wire waveguide at telecommunication wavelengths using femtosecond input pulse with energy lower than 5 pJ. Numerical modeling of pulse propagation in the waveguide, based on the experimentally characterized dispersion profile, shows that the supercontinuum is the result of soliton fission and dispersive wave generation. It is demonstrated that the SC is highly coherent and that the waveguides do not suffer from material degradation under femtosecond pulse illumination. Finally, a direct comparison of SC generation in c-Si and a-Si:H waveguides confirms the higher performances of a-Si:H over c-Si for broadband low power SC generation at telecommunication wavelengths.

  1. Hydrogen Generation Through Renewable Energy Sources at the NASA Glenn Research Center

    Science.gov (United States)

    Colozza, Anthony; Prokopius, Kevin

    2007-01-01

    An evaluation of the potential for generating high pressure, high purity hydrogen at the NASA Glenn Research Center (GRC) was performed. This evaluation was based on producing hydrogen utilizing a prototype Hamilton Standard electrolyzer that is capable of producing hydrogen at 3000 psi. The present state of the electrolyzer system was determined to identify the refurbishment requirements. The power for operating the electrolyzer would be produced through renewable power sources. Both wind and solar were considered in the analysis. The solar power production capability was based on the existing solar array field located at NASA GRC. The refurbishment and upgrade potential of the array field was determined and the array output was analyzed with various levels of upgrades throughout the year. The total available monthly and yearly energy from the array was determined. A wind turbine was also sized for operation. This sizing evaluated the wind potential at the site and produced an operational design point for the wind turbine. Commercially available wind turbines were evaluated to determine their applicability to this site. The system installation and power integration were also addressed. This included items such as housing the electrolyzer, power management, water supply, gas storage, cooling and hydrogen dispensing.

  2. Simultaneous Hydrogen Generation and Waste Acid Neutralization in a Reverse Electrodialysis System

    KAUST Repository

    Hatzell, Marta C.

    2014-09-02

    Waste acid streams produced at industrial sites are often co-located with large sources of waste heat (e.g., industrial exhaust gases, cooling water, and heated equipment). Reverse electrodialysis (RED) systems can be used to generate electrical power and hydrogen gas using waste heat-derived solutions, but high electrode overpotentials limit system performance. We show here that an ammonium bicarbonate (AmB) RED system can achieve simultaneous waste acid neutralization and in situ hydrogen production, while capturing energy from excess waste heat. The rate of acid neutralization was dependent on stack flow rate and increased 50× (from 0.06 ± 0.04 to 3.0 ± 0.32 pH units min -1 m-2 membrane), as the flow rate increased 6× (from 100 to 600 mL min-1). Acid neutralization primarily took place due to ammonium electromigration (37 ± 4%) and proton diffusion (60 ± 5%). The use of a synthetic waste acid stream as a catholyte (pH ≈ 2) also increased hydrogen production rates by 65% (from 5.3 ± 0.5 to 8.7 ± 0.1 m3 H2 m-3 catholyte day -1) compared to an AmB electrolyte (pH ≈ 8.5). These findings highlight the potential use of dissimilar electrolytes (e.g., basic anolyte and acidic catholyte) for enhanced power and hydrogen production in RED stacks. © 2014 American Chemical Society.

  3. Graphene Porous Foam Loaded with Molybdenum Carbide Nanoparticulate Electrocatalyst for Effective Hydrogen Generation.

    Science.gov (United States)

    Wang, Jie; Xia, Han; Peng, Zhen; Lv, Cuncai; Jin, Lihuang; Zhao, Yaoxing; Huang, Zhipeng; Zhang, Chi

    2016-04-21

    A facile method is developed for the synthesis of graphene porous foam (Gr PF) loaded with dispersed molybdenum carbide (Mo2 C) nanoparticles; the material exhibits effective catalytic activity in the hydrogen evolution reaction (HER). Mo2 C/Gr PF is synthesized by the carbonization of glucose and the carbothermal reduction of hexaammonium molybdate in a confined space defined by the intervals between sodium chloride nanoparticles. The synthesis in the confined space results in thin Gr PF (≈8 nm) loaded with aggregation-free small Mo2 C nanoparticles [(13±2) nm]. The overpotential required for a current density of 20 mA cm(-2) in the electrochemical hydrogen generation is as small as 199 mV in acidic solution and 380 mV in basic solution. The performance is superior to that of a Mo2 C/C composite and compares favorably to those reported for Mo2 C nanostructures. The Mo2 C/Gr PF affords stable water electrolysis in both acidic and basic solution and exhibits nearly 100 % faradaic efficiency. The prominent performance, long-term stability, and high faradic efficiency make Mo2 C/Gr PF a promising HER catalyst for practical hydrogen generation from water electrolysis.

  4. Study of hydrogen generation plant coupled to high temperature gas cooled reactor

    Science.gov (United States)

    Brown, Nicholas Robert

    Hydrogen generation using a high temperature nuclear reactor as a thermal driving vector is a promising future option for energy carrier production. In this scheme, the heat from the nuclear reactor drives an endothermic water-splitting plant, via coupling, through an intermediate heat exchanger. While both high temperature nuclear reactors and hydrogen generation plants have high individual degrees of development, study of the coupled plant is lacking. Particularly absent are considerations of the transient behavior of the coupled plant, as well as studies of the safety of the overall plant. The aim of this document is to contribute knowledge to the effort of nuclear hydrogen generation. In particular, this study regards identification of safety issues in the coupled plant and the transient modeling of some leading candidates for implementation in the Nuclear Hydrogen Initiative (NHI). The Sulfur Iodine (SI) and Hybrid Sulfur (HyS) cycles are considered as candidate hydrogen generation schemes. Several thermodynamically derived chemical reaction chamber models are coupled to a well-known reference design of a high temperature nuclear reactor. These chemical reaction chamber models have several dimensions of validation, including detailed steady state flowsheets, integrated loop test data, and bench scale chemical kinetics. Eight unique case studies are performed based on a thorough literature review of possible events. The case studies are: (1) feed flow failure from one section of the chemical plant to another, (2) product flow failure (recycle) within the chemical plant, (3) rupture or explosion within the chemical plant, (4) nuclear reactor helium inlet overcooling due to a process holding tank failure, (5) helium inlet overcooling as an anticipated transient without SCRAM, (6) total failure of the chemical plant, (7) parametric study of the temperature in an individual reaction chamber, and (8) control rod insertion in the nuclear reactor. Various parametric

  5. Co-generation of acetylene and hydrogen for a carbide-based fuel system

    Energy Technology Data Exchange (ETDEWEB)

    Carreiro, Louis G.; Burke, A. Alan [Naval Undersea Warfare Center Division Newport, Code 8231, 1176 Howell Street, Newport, RI 02841 (United States); Dubois, Lily [Stonehill College, Department of Chemistry, 320 Washington Street, Easton, MA 02357 (United States)

    2010-09-15

    The co-generation of acetylene and hydrogen from the hydrolysis of calcium carbide and calcium hydride was investigated as part of a unique carbide-based fuel system intended for high-temperature fuel cells. To gain better control of this highly energetic reaction, glycerin was used to coat the reactant particles to form slurry prior to their reaction with water. This process was shown to moderate the rate of gas production, as well as to provide a means for preparing slurry that could be pumped into the reactor vessel. It was also observed that the presence of calcium hydroxide, a by-product of hydrolysis, lowered the solubility of acetylene resulting in a higher initial flow rate due to less acetylene being dissolved in solution. However, the buildup of calcium hydroxide with time inhibited the hydrolysis of both calcium carbide and calcium hydride causing the acetylene and hydrogen flow rates to decrease. (author)

  6. Carbon quantum dots coated BiVO{sub 4} inverse opals for enhanced photoelectrochemical hydrogen generation

    Energy Technology Data Exchange (ETDEWEB)

    Nan, Feng; Shen, Mingrong; Fang, Liang, E-mail: zhkang@suda.edu.cn, E-mail: lfang@suda.edu.cn [College of Physics, Optoelectronics and Energy and Jiangsu Key Laboratory of Thin Films, Soochow University, Suzhou 215006 (China); Kang, Zhenhui, E-mail: zhkang@suda.edu.cn, E-mail: lfang@suda.edu.cn [Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-based Functional Materials and Devices, and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Wang, Junling [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore)

    2015-04-13

    Carbon quantum dots (CQDs) coated BiVO{sub 4} inverse opal (io-BiVO{sub 4}) structure that shows dramatic improvement of photoelectrochemical hydrogen generation has been fabricated using electrodeposition with a template. The io-BiVO{sub 4} maximizes photon trapping through slow light effect, while maintaining adequate surface area for effective redox reactions. CQDs are then incorporated to the io-BiVO{sub 4} to further improve the photoconversion efficiency. Due to the strong visible light absorption property of CQDs and enhanced separation of the photoexcited electrons, the CQDs coated io-BiVO{sub 4} exhibit a maximum photo-to-hydrogen conversion efficiency of 0.35%, which is 6 times higher than that of the pure BiVO{sub 4} thin films. This work is a good example of designing composite photoelectrode by combining quantum dots and photonic crystal.

  7. Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R.; Chang, Christopher J.; Karunadasa, Hemamala I.; Majda, Marcin

    2016-04-19

    New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS.sub.2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W.sub.2)MoS.sub.2].sup.x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H.sub.2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H.sub.2 per mole of catalyst.

  8. Performance of laboratory polymer electrolyte membrane hydrogen generator with sputtered iridium oxide anode

    Science.gov (United States)

    Labou, D.; Slavcheva, E.; Schnakenberg, U.; Neophytides, S.

    The continuous improvement of the anode materials constitutes a major challenge for the future commercial use of polymer electrolyte membranes (PEM) electrolyzers for hydrogen production. In accordance to this direction, iridium/titanium films deposited directly on carbon substrates via magnetron sputtering are operated as electrodes for the oxygen evolution reaction interfaced with Nafion 115 electrolyte in a laboratory single cell PEM hydrogen generator. The anode with 0.2 mg cm -2 Ir catalyst loading was electrochemically activated by cycling its potential value between 0 and 1.2 V (vs. RHE). The water electrolysis cell was operated at 90 °C with current density 1 A cm -2 at 1.51 V without the ohmic contribution. The corresponding current density per mgr of Ir catalyst is 5 A mg -1. The achieved high efficiency is combined with sufficient electrode stability since the oxidation of the carbon substrate during the anodic polarization is almost negligible.

  9. Experimental Study of Plasma Under-liquid Electrolysis in Hydrogen Generation

    Institute of Scientific and Technical Information of China (English)

    严宗诚; 陈砺; 王红林

    2006-01-01

    The application and characteristics of relatively big volume plasma produced with cathodic glow discharges taking place across a gaseous envelope over the cathode which was dipped into electrolyte in hydrogen generation were studied. A critical investigation of the influence of methanol concentration and voltage across the circuit on the composition and power consumption per cubic meter of cathode liberating gas was carried out. The course of plasma under-liquid electrolysis has the typical characteristics of glow discharge electrolysis. The cathode liberating gas was in substantial excess of the Faraday law value. When the voltage across the circuit was equal to 550 V, the volume of cathodic gas with sodium carbonate solution was equal to 16.97 times the Faraday law value. The study showed that methanol molecules are more active than water molecules.The methanol molecules were decomposed at the plasma-catholyte interface by the radicals coming out the plasma mantle.Energy consumption per cubic meter of cathodic gases (WV) decreased while methanol concentration of the electrolytes increased. When methanol concentration equaled 5% (ψ), WV was 10.381×103 kJ/m3, less than the corresponding theoretic value of conventional water electrolysis method. The cathodic liberating gas was a mixture of hydrogen, carbon dioxide and carbon monoxide with over 95% hydrogen, if methanol concentration was more than 15% (ψ). The present research work revealed an innovative application of glow discharge and a new highly efficient hydrogen generation method, which depleted less resource and energy than normal electrolysis and is environmentally friendly.

  10. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-29

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  11. [Russian oxygen generation system "Elektron-VM": hydrogen content in electrolytically produced oxygen for breathing by International Space Station crews].

    Science.gov (United States)

    Proshkin, V Yu; Kurmazenko, E A

    2014-01-01

    The article presents the particulars of hydrogen content in electrolysis oxygen produced aboard the ISS Russian segment by oxygen generator "Elektron-VM" (SGK) for crew breathing. Hydrogen content was estimated as in the course of SGK operation in the ISS RS, so during the ground life tests. According to the investigation of hydrogen sources, the primary path of H2 appearance in oxygen is its diffusion through the porous diaphragm separating the electrolytic-cell cathode and anode chambers. Effectiveness of hydrogen oxidation in the SGK reheating unit was evaluated.

  12. Classical Dynamics of Harmonic Generation of the Hydrogen Molecular Ion Interacting with Ultrashort Intense Laser Pulses

    Institute of Scientific and Technical Information of China (English)

    LI Chao-Hong; DUAN Yi-Wu; Wing-Ki Liu; Jian-Min Yuan

    2001-01-01

    Within Born-Oppenheimer approximation, by using the classical trajectory theory, a description for the high order harmonic generation of the hydrogen molecular ion interacting with ultrashort laser pulses has been pre sented. The Coulomb singularities have been remedied by the regularization. The action-angle variables have been used to generate the initial inversion symmetry microcanonical distribution. Within a proper intensity range, a harmonic plateau with only odd harmonics appears. For a larger intensity, because of the existence of chaos, the harmonic spectra become noisier. For a large enough intensity, the ionization takes place and the harmonics disappear. So the chaos causes the noises, the ionization suppresses the harmonic generation, and the onset of the ionization follows the onset of chaos.

  13. Improvement of the efficiency of a space oxygen-hydrogen electrochemical generator

    Science.gov (United States)

    Glukhikh, I. N.; Shcherbakov, A. N.; Chelyaev, V. F.

    2014-12-01

    This paper describes the method used for cooling of an on-board oxygen-hydrogen electrochemical generator (ECG). Apart from electric power, such a unit produces water of reaction and heat; the latter is an additional load on the thermal control system of a space vehicle. This load is undesirable in long-duration space flights, when specific energy characteristics of on-board systems are the determining factors. It is suggested to partially compensate the energy consumption by the thermal control system of a space vehicle required for cooling of the electrochemical generator through evaporation of water of reaction from the generator into a vacuum (or through ice sublimation if the pressure in the ambient space is lower than that in the triple point of water.) Such method of cooling of an electrochemical generator improves specific energy parameters of an on-board electric power supply system, and, due to the presence of the negative feedback, it makes the operation of this system more stable. Estimates suggest that it is possible to compensate approximately one half of heat released from the generator through evaporation of its water of reaction at the electrical efficiency of the electrochemical generator equal to 60%. In this case, even minor increase in the efficiency of the generator would result in a considerable increase in the efficiency of the evaporative system intended for its cooling.

  14. Elimination Of Catalytic Hydrogen Generation In Defense Waste Processing Facility Slurries

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D. C.

    2013-01-22

    Based on lab-scale simulations of Defense Waste Processing Facility (DWPF) slurry chemistry, the addition of sodium nitrite and sodium hydroxide to waste slurries at concentrations sufficient to take the aqueous phase into the alkaline region (pH > 7) with approximately 500 mg nitrite ion/kg slurry (assuming <25 wt% total solids, or equivalently 2,000 mg nitrite/kg total solids) is sufficient to effectively deactivate the noble metal catalysts at temperatures between room temperature and boiling. This is a potential strategy for eliminating catalytic hydrogen generation from the list of concerns for sludge carried over into the DWPF Slurry Mix Evaporator Condensate Tank (SMECT) or Recycle Collection Tank (RCT). These conclusions are drawn in large part from the various phases of the DWPF catalytic hydrogen generation program conducted between 2005 and 2009. The findings could apply to various situations, including a solids carry-over from either the Sludge Receipt and Adjustment Tank (SRAT) or Slurry Mix Evaporator (SME) into the SMECT with subsequent transfer to the RCT, as well as a spill of formic acid into the sump system and transfer into an RCT that already contains sludge solids. There are other potential mitigating factors for the SMECT and RCT, since these vessels are typically operated at temperatures close to the minimum temperatures that catalytic hydrogen has been observed to occur in either the SRAT or SME (pure slurry case), and these vessels are also likely to be considerably more dilute in both noble metals and formate ion (the two essential components to catalytic hydrogen generation) than the two primary process vessels. Rhodium certainly, and ruthenium likely, are present as metal-ligand complexes that are favored under certain concentrations of the surrounding species. Therefore, in the SMECT or RCT, where a small volume of SRAT or SME material would be significantly diluted, conditions would be less optimal for forming or sustaining the

  15. Development and performance of bench-scale reactor for the photocatalytic generation of hydrogen

    International Nuclear Information System (INIS)

    In this study, a new novel bench-scale (5 L) tubular photocatalytic reactor was developed and its feasibility studies were conducted for optimizing the operating variables, namely concentration of sulfide ion, concentration of sulfite ion, pH, catalyst concentration, lamp power, volume of wastewater and recycle flow rates at batch recycle mode for the generation of hydrogen from aqueous sodium sulfide using CdS–ZnS/TiO2 core–shell NPs (nanoparticles). The maximum H2 generation was found at 0.05 M concentration of sulfide ion, 0.2 M concentration of sulfite ion, pH 11.3, 0.5 g/L catalyst concentration and recycle flow rate of 18 L/h. Reusability studies were conducted for analyzing stability of photocatalyst. The results showed that the generation of hydrogen depends on light intensity, photoreactor used, nature of photocatalysts and the operating conditions. - Highlights: • Clean fuel production using solar energy. • Bench-scale tubular photocatalytic reactor was developed. • Operating variables have significant effect

  16. Hydrogen

    OpenAIRE

    John O’M. Bockris

    2011-01-01

    The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the...

  17. Comparison of hydrogen production and electrical power generation for energy capture in closed-loop ammonium bicarbonate reverse electrodialysis systems

    KAUST Repository

    Hatzell, Marta C.

    2014-01-01

    Currently, there is an enormous amount of energy available from salinity gradients, which could be used for clean hydrogen production. Through the use of a favorable oxygen reduction reaction (ORR) cathode, the projected electrical energy generated by a single pass ammonium bicarbonate reverse electrodialysis (RED) system approached 78 W h m-3. However, if RED is operated with the less favorable (higher overpotential) hydrogen evolution electrode and hydrogen gas is harvested, the energy recovered increases by as much ∼1.5× to 118 W h m-3. Indirect hydrogen production through coupling an RED stack with an external electrolysis system was only projected to achieve 35 W h m-3 or ∼1/3 of that produced through direct hydrogen generation.

  18. Hydrogen generation arising from the {sup 59}Ni(n,p) reaction and its impact on fission-fusion correlations

    Energy Technology Data Exchange (ETDEWEB)

    Greenwood, L.R.; Garner, A.F.

    1996-04-01

    Whilte the influence of transmutant helium on radiation-induced microstructural evolution has often been studied, there is a tendency to overlook the influence of concurrently-generated hydrogen. There have been some recent speculation and studies, however, that suggest that the influence of hydrogen may be enhanced in the presence of large amounts of helium, especially at lower irradiation temperatures typical of projected ITER operation. The impact of the (n,p) reaction on both hydrogen generation rates and displacement rates are evaluated in this paper for a variety of neutron spectra employed in fission-fusion correlation.

  19. [Isolation of a high hydrogen-producing mutant TB34 generated by transposon insertion and analysis of hydrogen production].

    Science.gov (United States)

    Liu, Hong-Yan; Wang, Guang-Ce; Shi, Liu-Yang; Zhu, Da-Ling

    2012-07-01

    To increase the hydrogen-producing capacity of Pantoea agglomerans BH18, isolated from mangrove sludge, we constructed a stable transposon mutagenesis library of this strain. A Tn7-based transposon was randomly inserted into the genomic DNA. Mutants were screened by kanamycin resistance and identified by amplification of the inserted transposon sequences. A mutant strain TB34 was isolated, whose hydrogen production capacity was significantly improved compared to the wild type strain. In seawater-containing medium supplemented with 10 g x L(-1) glucose and had an initial pH of 7.0, the hydrogen yield (H2/glucose) of the mutant strain was (2.04 +/- 0.04) mol x mol(-1), which was 43% higher than that of the wild type strain. The mutant TB34 showed steady hydrogen production capacity for five consecutive passages. Different carbon sources were tested in the hydrogen production by the mutant TB34 and the results showed that both the mutant strain TB34 and the wild type strain BH18 were able to produce hydrogen on sucrose, glucose and fructose. However, different from the wild type strain, the mutant strain TB34 was also able to produce hydrogen using xylose as substrate, with a hydrogen yield (H2/xylose) of (1.34 +/- 0.09) mol x mol(-1), indicating a broader substrate spectrum in the mutant.

  20. Batch sodium borohydride hydrolysis systems: Effect of sudden valve opening on hydrogen generation rate

    OpenAIRE

    M. J. F. Ferreira; Coelho, F; Rangel, C. M.; Pinto, A. M. F. R.

    2012-01-01

    A study was undertaken in order to investigate the potential of hydrogen (H 2) generation by hydrolysis of sodium borohydride solution (10 wt% NaBH 4 and 7 wt% NaOH), in batch reactors, operating at moderate pressures (up to #8764;1.2 MPa), in the presence of a powdered nickel-ruthenium based catalyst, reused between 311 and 316 times, to feed on-demand a proton exchange membrane fuel cell. A different approach to the testing of the performance of the batch NaBH 4 hydrolysis system is explore...

  1. Investigation of cold cathodes of plasma sources generating of hydrogen ion beams

    CERN Document Server

    Veresov, L P; Dzkuya, M I; Zhukov, Y N; Kuznetsov, G V; Tsekvava, I A

    2001-01-01

    Designs of a hollow cellular cathode (HCC) and of an inverse cylindrical multichamber magnetronic cathode (ICMMC), used as cold cathodes in duoplasmatron for hydrogen ion beam generation, are described. Their service characteristics are compared. It is ascertained that emission ability of both HCC and ICMMC is approximately the same. However, duoplasmatron with ICMMC features a three times higher gas effectiveness compared with HCC. Service life of duoplasmatron with both types of cathodes amounts to several thousand hours. On the basis of test results the choice is made in favour of ICMMC

  2. Room temperature hydrogen generation from hydrolysis of ammonia-borane over an efficient NiAgPd/C catalyst

    KAUST Repository

    Hu, Lei

    2014-12-01

    NiAgPd nanoparticles are successfully synthesized by in-situ reduction of Ni, Ag and Pd salts on the surface of carbon. Their catalytic activity was examined in ammonia borane (NH3BH3) hydrolysis to generate hydrogen gas. This nanomaterial exhibits a higher catalytic activity than those of monometallic and bimetallic counterparts and a stoichiometric amount of hydrogen was produced at a high generation rate. Hydrogen production rates were investigated in different concentrations of NH3BH3 solutions, including in the borates saturated solution, showing little influence of the concentrations on the reaction rates. The hydrogen production rate can reach 3.6-3.8 mol H2 molcat -1 min-1 at room temperature (21 °C). The activation energy and TOF value are 38.36 kJ/mol and 93.8 mol H2 molcat -1 min-1, respectively, comparable to those of Pt based catalysts. This nanomaterial catalyst also exhibits excellent chemical stability, and no significant morphology change was observed from TEM after the reaction. Using this catalyst for continuously hydrogen generation, the hydrogen production rate can be kept after generating 6.2 L hydrogen with over 10,000 turnovers and a TOF value of 90.3 mol H2 molcat -1 min-1.

  3. Role of hydrogen generation by Klebsiella pneumoniae in the oral cavity.

    Science.gov (United States)

    Kanazuru, Tomoko; Sato, Eisuke F; Nagata, Kumiko; Matsui, Hiroshi; Watanabe, Kunihiko; Kasahara, Emiko; Jikumaru, Mika; Inoue, June; Inoue, Masayasu

    2010-12-01

    Some gastrointestinal bacteria synthesize hydrogen (H(2)) by fermentation. Despite the presence of bactericidal factors in human saliva, a large number of bacteria also live in the oral cavity. It has never been shown that oral bacteria also produce H(2) or what role H(2) might play in the oral cavity. It was found that a significant amount of H(2) is synthesized in the oral cavity of healthy human subjects, and that its generation is enhanced by the presence of glucose but inhibited by either teeth brushing or sterilization with povidone iodine. These observations suggest the presence of H(2)-generating bacteria in the oral cavity. The screening of commensal bacteria in the oral cavity revealed that a variety of anaerobic bacteria generate H(2). Among them, Klebsiella pneumoniae (K. pneumoniae) generated significantly large amounts of H(2) in the presence of glucose. Biochemical analysis revealed that various proteins in K. pneumoniae are carbonylated under standard culture conditions, and that oxidative stress induced by the presence of Fe(++) and H(2)O(2) increases the number of carbonylated proteins, particularly when their hydrogenase activity is inhibited by KCN. Inhibition of H(2) generation markedly suppresses the growth of K. pneumoniae. These observations suggest that H(2) generation and/or the reduction of oxidative stress is important for the survival and growth of K. pneumoniae in the oral cavity.

  4. Effective regimes of runaway electron beam generation in helium, hydrogen, and nitrogen

    Science.gov (United States)

    Tarasenko, V. F.; Baksht, E. Kh.; Burachenko, A. G.; Lomaev, M. I.; Sorokin, D. A.; Shut'ko, Yu. V.

    2010-04-01

    Runaway electron beam parameters and current-voltage characteristics of discharge in helium, hydrogen, and nitrogen at pressures in the range of several Torr to several hundred Torr have been studied. It is found that the maximum amplitudes of supershort avalanche electron beams (SAEBs) with a pulse full width at half maximum (FWHM) of ˜100 ps are achieved in helium, hydrogen, and nitrogen at a pressure of ˜60, ˜30, and ˜10 Torr, respectively. It is shown that, as the gas pressure is increased in the indicated range, the breakdown voltage of the gas-filled gap decreases, which leads to a decrease in the SAEB current amplitude. At pressures of helium within 20-60 Torr, hydrogen within 10-30 Torr, and nitrogen within 3-10 Torr, the regime of the runaway electron beam generation changes and, by varying the pressure in the gas-filled diode in the indicated intervals, it is possible to smoothly control the current pulse duration (FWHM) from ˜100 to ˜500 ps, while the beam current amplitude increases by a factor of 1.5-3.

  5. Research progress of olefins asymmetric hydrogenation catalyzed by rhodium catalysts%铑催化剂催化烯烃不对称加氢反应研究进展

    Institute of Scientific and Technical Information of China (English)

    王红琴; 蒋丽红; 王亚明

    2016-01-01

    不对称催化氢化反应具有完美的原子经济性和清洁高效等特点,是最受青睐的不对称合成方法之一。C=C、C=O、C=N 的不对称加氢反应仍主要依赖过渡金属催化剂。过渡金属催化剂,尤其是铑催化剂,催化碳碳双键的不对称加氢反应仍是一个不断发展的领域。本文对近年来利用铑催化剂催化烯烃进行不对称氢化反应的研究进展进行了综述,着重介绍了铑-双膦配体催化体系催化烯烃不对称加氢反应的催化机理,以及铑催化剂在烯胺、不饱和羧酸及衍生物、烯醇酯和非官能团烯烃不对称氢化中的应用,并通过对现有文献的总结指出了今后铑催化剂催化烯烃氢化反应的研究重点,即:①铑-单膦配体催化烯烃不对称氢化反应的作用机理须待提出;②非官能化底物不对称催化氢化反应的手性配体亟待拓宽。%Asymmetric hydrogenation has the advantage of cleanliness,perfect atom economy,and is one of the hottest methods of asymmetric synthesis. The asymmetric hydrogenation in C=C,C=O, C=N are still primarily dependent on the use of transition metal catalysts. The study of transition metal catalysts,especially the asymmetric hydrogenation of carbon-carbon double bond catalyzed by rhodium catalysts is still an evolving field. In the present review,the progress on asymmetric hydrogenation of olefins catalyzed by rhodium catalysts are described,including the catalytic mechanism of rhodium-diphosphine ligand catalyst system,the application of asymmetric hydrogenation of enamines,unsaturated carboxylic acids and their derivatives,enol ester as well as unfunctionalized olefins catalyzed by rhodium catalysts. The development trend of rhodium catalysts for asymmetric hydrogenation of olefins was pointed out. For instance:① the catalytic mechanism of asymmetric hydrogenation of olefins by rhodium-monophosphine ligand needs to be understood;②more chiral ligands for

  6. Hydrogen Generation from Biomass-Derived Surgar Alcohols via the Aqueous-Phase Carbohydrate Reforming (ACR) Process

    Energy Technology Data Exchange (ETDEWEB)

    Randy Cortright

    2006-06-30

    This project involved the investigation and development of catalysts and reactor systems that will be cost-effective to generate hydrogen from potential sorbitol streams. The intention was to identify the required catalysts and reactors systems as well as the design, construction, and operation of a 300 grams per hour hydrogen system. Virent was able to accomplish this objective with a system that generates 2.2 kgs an hour of gas containing both hydrogen and alkanes that relied directly on the work performed under this grant. This system, funded in part by the local Madison utility, Madison, Gas & Electric (MGE), is described further in the report. The design and development of this system should provide the necessary scale-up information for the generation of hydrogen from corn-derived sorbitol.

  7. Hydrogen

    Directory of Open Access Journals (Sweden)

    John O’M. Bockris

    2011-11-01

    Full Text Available The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan. Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  8. Hydrogen peroxide generation by the Weissberger biogenic oxidative system during hyaluronan degradation.

    Science.gov (United States)

    Valachová, Katarina; Topoľská, Dominika; Mendichi, Raniero; Collins, Maurice N; Sasinková, Vlasta; Šoltés, Ladislav

    2016-09-01

    By applying the enzyme catalase, our study on hyaluronan degradation confirms the generation of hydrogen peroxide using the Weissberger biogenic oxidative system (WBOS), which is composed of ascorbate and cupric ions. Dynamic viscosities of hyaluronan (HA) solutions influenced by WBOS in the absence and presence of catalase were analysed by rotational viscometry. Molar masses of HAs were determined by size-exclusion chromatography with multi-angle laser-light scattering. Our results show that catalase dose-dependently inhibited the degradation of HA macromolecules, which presumably confirms the generation of H2O2 in the reaction system. This has implications in range of biomedical applications such as arthritic joint treatment, tissue engineering, ocular and cosmetic surgery. PMID:27185130

  9. Synthesis and Characterization of K-Ta Mixed Oxides for Hydrogen Generation in Photocatalysis

    Directory of Open Access Journals (Sweden)

    Beata Zielińska

    2012-01-01

    Full Text Available K-Ta mixed oxides photocatalysts have been prepared by impregnation followed by calcination. The influence of the reaction temperature (450°C–900°C on the phase formation, crystal morphology, and photocatalytic activity in hydrogen generation of the produced materials was investigated. The detailed analysis has revealed that all products exhibit high crystallinity and irregular structure. Moreover, two different crystal structures of potassium tantalates such as KTaO3 and K2Ta4O11 were obtained. It was also found that the sample composed of KTaO3 and traces of unreacted Ta2O5 (annealed at 600°C exhibits the highest activity in the reaction of photocatalytic hydrogen generation. The crystallographic phases, optical and vibronic properties were examined by X-ray diffraction (XRD and diffuse reflectance (DR UV-vis and resonance Raman spectroscopic methods, respectively. Morphology and chemical composition of the produced samples were studied using a high-resolution transmission electron microscope (HR-TEM and an energy dispersive X-ray spectrometer (EDX as its mode.

  10. Hydrogen sensor

    Science.gov (United States)

    Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

    2010-11-23

    A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

  11. Temperature-programmed desorption of hydrogen from platinum particles on {gamma}-Al{sub 2}O{sub 3}: Evidence of platinum-catalyzed dehydroxylation of {gamma}-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Alexeev, O.; Kim, D.W.; Gates, B.C. [Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering and Materials Science; Graham, G.W.; Shelef, M. [Ford Motor Co., Dearborn, MI (United States)

    1999-07-01

    Samples of Pt on {gamma}-Al{sub 2}O{sub 3} were prepared by reduction in H{sub 2} at 400 C of [PtCl{sub 2}(PhCN){sub 2}], adsorbed intact from n-pentane solution onto {gamma}-Al{sub 2}O{sub 3} powder that had been partially dehydroxylated under vacuum at 400 C. The Pt dispersion was determined to be about 0.58 by standard methods, namely, chemisorption of hydrogen, of oxygen, and of CO, titration of chemisorbed oxygen with hydrogen, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The supported Pt particles were resistant to sintering in the presence of O{sub 2} at temperatures up to 400 C, as shown by chemisorption and EXAFS data, but the latter indicated that a combination of O{sub 2} and H{sub 2} treatments at 200--400 C led to changes in particle morphology. The samples were investigated by temperature-programmed desorption (TPD) of preadsorbed hydrogen; a TPD peak centered at 120 C represents hydrogen adsorbed on Pt and confirms the value of 0.58 for the dispersion. TPD of preadsorbed H{sub 2} gave evidence of a second desorption peak, at 580 C, which was always accompanied by desorption of water at the same temperature; its presence was found to depend chiefly on the sample reduction temperature and evacuation time (it was absent when there was no Pt on the {gamma}-Al{sub 2}O{sub 3}). The desorption of H{sub 2} or D{sub 2} that had been adsorbed on Pt/{gamma}-Al{sub 2}O{sub 3} reduced with D{sub 2} or H{sub 2}, respectively, shows that hydrogen species desorbed at about 580 C originate from water (hydroxyl) species as a result of Pt-catalyzed decomposition.

  12. Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power

    International Nuclear Information System (INIS)

    OAK B188 Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power There is currently no large scale, cost-effective, environmentally attractive hydrogen production process, nor is such a process available for commercialization. Hydrogen is a promising energy carrier, which potentially could replace the fossil fuels used in the transportation sector of our economy. Fossil fuels are polluting and carbon dioxide emissions from their combustion are thought to be responsible for global warming. The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high temperature heat from an advanced nuclear power station. Almost 800 literature references were located which pertain to thermochemical production of hydrogen from water and over 100 thermochemical watersplitting cycles were examined. Using defined criteria and quantifiable metrics, 25 cycles have been selected for more detailed study

  13. Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power

    Energy Technology Data Exchange (ETDEWEB)

    Brown, L.C.; Funk, J.F.; Showalter, S.K.

    1999-12-15

    OAK B188 Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power There is currently no large scale, cost-effective, environmentally attractive hydrogen production process, nor is such a process available for commercialization. Hydrogen is a promising energy carrier, which potentially could replace the fossil fuels used in the transportation sector of our economy. Fossil fuels are polluting and carbon dioxide emissions from their combustion are thought to be responsible for global warming. The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high temperature heat from an advanced nuclear power station. Almost 800 literature references were located which pertain to thermochemical production of hydrogen from water and over 100 thermochemical watersplitting cycles were examined. Using defined criteria and quantifiable metrics, 25 cycles have been selected for more detailed study.

  14. Hydrogen Peroxide-Resistant CotA and YjqC of Bacillus altitudinis Spores Are a Promising Biocatalyst for Catalyzing Reduction of Sinapic Acid and Sinapine in Rapeseed Meal

    Science.gov (United States)

    Zhang, Yanzhou; Li, Xunhang; Hao, Zhikui; Xi, Ruchun; Cai, Yujie; Liao, Xiangru

    2016-01-01

    For the more efficient detoxification of phenolic compounds, a promising avenue would be to develop a multi-enzyme biocatalyst comprising peroxidase, laccase and other oxidases. However, the development of this multi-enzyme biocatalyst is limited by the vulnerability of fungal laccases and peroxidases to hydrogen peroxide (H2O2)-induced inactivation. Therefore, H2O2-resistant peroxidase and laccase should be exploited. In this study, H2O2-stable CotA and YjqC were isolated from the outer coat of Bacillus altitudinis SYBC hb4 spores. In addition to the thermal and alkali stability of catalytic activity, CotA also exhibited a much higher H2O2 tolerance than fungal laccases from Trametes versicolor and Trametes trogii. YjqC is a sporulation-related manganese (Mn) catalase with striking peroxidase activity for sinapic acid (SA) and sinapine (SNP). In contrast to the typical heme-containing peroxidases, the peroxidase activity of YjqC was also highly resistant to inhibition by H2O2 and heat. CotA could also catalyze the oxidation of SA and SNP. CotA had a much higher affinity for SA than B. subtilis CotA. CotA and YjqC rendered from B. altitudinis spores had promising laccase and peroxidase activities for SA and SNP. Specifically, the B. altitudinis spores could be regarded as a multi-enzyme biocatalyst composed of CotA and YjqC. The B. altitudinis spores were efficient for catalyzing the degradation of SA and SNP in rapeseed meal. Moreover, efficiency of the spore-catalyzed degradation of SA and SNP was greatly improved by the presence of 15 mM H2O2. This effect was largely attributed to synergistic biocatalysis of the H2O2-resistant CotA and YjqC toward SA and SNP. PMID:27362423

  15. Hydrogen Peroxide-Resistant CotA and YjqC of Bacillus altitudinis Spores Are a Promising Biocatalyst for Catalyzing Reduction of Sinapic Acid and Sinapine in Rapeseed Meal.

    Directory of Open Access Journals (Sweden)

    Yanzhou Zhang

    Full Text Available For the more efficient detoxification of phenolic compounds, a promising avenue would be to develop a multi-enzyme biocatalyst comprising peroxidase, laccase and other oxidases. However, the development of this multi-enzyme biocatalyst is limited by the vulnerability of fungal laccases and peroxidases to hydrogen peroxide (H2O2-induced inactivation. Therefore, H2O2-resistant peroxidase and laccase should be exploited. In this study, H2O2-stable CotA and YjqC were isolated from the outer coat of Bacillus altitudinis SYBC hb4 spores. In addition to the thermal and alkali stability of catalytic activity, CotA also exhibited a much higher H2O2 tolerance than fungal laccases from Trametes versicolor and Trametes trogii. YjqC is a sporulation-related manganese (Mn catalase with striking peroxidase activity for sinapic acid (SA and sinapine (SNP. In contrast to the typical heme-containing peroxidases, the peroxidase activity of YjqC was also highly resistant to inhibition by H2O2 and heat. CotA could also catalyze the oxidation of SA and SNP. CotA had a much higher affinity for SA than B. subtilis CotA. CotA and YjqC rendered from B. altitudinis spores had promising laccase and peroxidase activities for SA and SNP. Specifically, the B. altitudinis spores could be regarded as a multi-enzyme biocatalyst composed of CotA and YjqC. The B. altitudinis spores were efficient for catalyzing the degradation of SA and SNP in rapeseed meal. Moreover, efficiency of the spore-catalyzed degradation of SA and SNP was greatly improved by the presence of 15 mM H2O2. This effect was largely attributed to synergistic biocatalysis of the H2O2-resistant CotA and YjqC toward SA and SNP.

  16. Hydrogen Peroxide-Resistant CotA and YjqC of Bacillus altitudinis Spores Are a Promising Biocatalyst for Catalyzing Reduction of Sinapic Acid and Sinapine in Rapeseed Meal.

    Science.gov (United States)

    Zhang, Yanzhou; Li, Xunhang; Hao, Zhikui; Xi, Ruchun; Cai, Yujie; Liao, Xiangru

    2016-01-01

    For the more efficient detoxification of phenolic compounds, a promising avenue would be to develop a multi-enzyme biocatalyst comprising peroxidase, laccase and other oxidases. However, the development of this multi-enzyme biocatalyst is limited by the vulnerability of fungal laccases and peroxidases to hydrogen peroxide (H2O2)-induced inactivation. Therefore, H2O2-resistant peroxidase and laccase should be exploited. In this study, H2O2-stable CotA and YjqC were isolated from the outer coat of Bacillus altitudinis SYBC hb4 spores. In addition to the thermal and alkali stability of catalytic activity, CotA also exhibited a much higher H2O2 tolerance than fungal laccases from Trametes versicolor and Trametes trogii. YjqC is a sporulation-related manganese (Mn) catalase with striking peroxidase activity for sinapic acid (SA) and sinapine (SNP). In contrast to the typical heme-containing peroxidases, the peroxidase activity of YjqC was also highly resistant to inhibition by H2O2 and heat. CotA could also catalyze the oxidation of SA and SNP. CotA had a much higher affinity for SA than B. subtilis CotA. CotA and YjqC rendered from B. altitudinis spores had promising laccase and peroxidase activities for SA and SNP. Specifically, the B. altitudinis spores could be regarded as a multi-enzyme biocatalyst composed of CotA and YjqC. The B. altitudinis spores were efficient for catalyzing the degradation of SA and SNP in rapeseed meal. Moreover, efficiency of the spore-catalyzed degradation of SA and SNP was greatly improved by the presence of 15 mM H2O2. This effect was largely attributed to synergistic biocatalysis of the H2O2-resistant CotA and YjqC toward SA and SNP. PMID:27362423

  17. Inhibition of hydrogen sulfide generation from disposed gypsum drywall using chemical inhibitors

    International Nuclear Information System (INIS)

    Disposal of gypsum drywall in landfills has been demonstrated to elevate hydrogen sulfide (H2S) concentrations in landfill gas, a problem with respect to odor, worker safety, and deleterious effect on gas-to-energy systems. Since H2S production in landfills results from biological activity, the concept of inhibiting H2S production through the application of chemical agents to drywall during disposal was studied. Three possible inhibition agents - sodium molybdate (Na2MoO4), ferric chloride (FeCl3), and hydrated lime (Ca(OH)2) - were evaluated using flask and column experiments. All three agents inhibited H2S generation, with Na2MoO4 reducing H2S generation by interrupting the biological sulfate reduction process and Ca(OH)2 providing an unfavorable pH for biological growth. Although FeCl3 was intended to provide an electron acceptor for a competing group of bacteria, the mechanism found responsible for inhibiting H2S production in the column experiment was a reduction in pH. Application of both Na2MoO4 and FeCl3 inhibited H2S generation over a long period (over 180 days), but the impact of Ca(OH)2 decreased with time as the alkalinity it contributed was neutralized by the generated H2S. Practical application and potential environmental implications need additional exploration.

  18. Inhibition of hydrogen sulfide generation from disposed gypsum drywall using chemical inhibitors.

    Science.gov (United States)

    Xu, Qiyong; Townsend, Timothy; Bitton, Gabriel

    2011-07-15

    Disposal of gypsum drywall in landfills has been demonstrated to elevate hydrogen sulfide (H(2)S) concentrations in landfill gas, a problem with respect to odor, worker safety, and deleterious effect on gas-to-energy systems. Since H(2)S production in landfills results from biological activity, the concept of inhibiting H(2)S production through the application of chemical agents to drywall during disposal was studied. Three possible inhibition agents - sodium molybdate (Na(2)MoO(4)), ferric chloride (FeCl(3)), and hydrated lime (Ca(OH)(2)) - were evaluated using flask and column experiments. All three agents inhibited H(2)S generation, with Na(2)MoO(4) reducing H(2)S generation by interrupting the biological sulfate reduction process and Ca(OH)(2) providing an unfavorable pH for biological growth. Although FeCl(3) was intended to provide an electron acceptor for a competing group of bacteria, the mechanism found responsible for inhibiting H(2)S production in the column experiment was a reduction in pH. Application of both Na(2)MoO(4) and FeCl(3) inhibited H(2)S generation over a long period (over 180 days), but the impact of Ca(OH)(2) decreased with time as the alkalinity it contributed was neutralized by the generated H(2)S. Practical application and potential environmental implications need additional exploration. PMID:21592650

  19. STANDALONE &LDQUO;GREEN&RDQUO; COMMUNITY-CENTER BUILDINGS: HYDROGEN GENERATION/STORAGE/DELIVERY SYSTEM FOR WHEN PRIMARY ENERGY STORAGE IS AT CAPACITY

    Science.gov (United States)

    Overall, the implementation of a computer-controlled hydrogen generation system and subsequent conversion of small engine equipment for hydrogen use has been surprisingly straightforward from an engineering and technology standpoint. More testing is required to get a better gr...

  20. Ruthenium-BINAP Catalyzed Alcohol C-H tert-Prenylation via 1,3-Enyne Transfer Hydrogenation: Beyond Stoichiometric Carbanions in Enantioselective Carbonyl Propargylation.

    Science.gov (United States)

    Nguyen, Khoa D; Herkommer, Daniel; Krische, Michael J

    2016-04-27

    The chiral ruthenium complex formed in situ from (TFA)2Ru(CO)(PPh3)2 and (R)-BINAP is found to catalyze the enantioselective C-C coupling of diverse primary alcohols with the 1,3-enyne, TMSC≡CC(Me)═CH2, to form secondary homopropargyl alcohols bearing gem-dimethyl groups. All reagents for this byproduct-free coupling are inexpensive and commercially available, making this protocol a practical alternative to stoichiometric carbanions in enantioselective carbonyl reverse prenylation. PMID:27079149

  1. Hydrogen generation from polyvinyl alcohol-contaminated wastewater by a process of supercritical water gasification

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Gasification of polyvinyl alcohol (PVA)-contaminated wastewater in supercritical water (SCW) was investigated in a continuous flow reactor at 723-873 K, 20-36 MPa and residence time of 20-60 s. The gas and liquid products were analyzed by GC/TCD, TOC analyzer and GC/MS. The main gas products were H2, CH4, CO and CO2. Pressure change had no significant influence on gasification efficiency. Higher temperature and longer residence time enhanced gasification efficiency, and lower temperature favored the production of H2. The effects of KOH catalyst on gas product composition were studied, and gasification efficiency were analyzed. The TOC removal efficiency (TOCR), carbon gasification ratio (CGR) and hydrogen gasification ratio (HGR) were up to 96.00%, 95.92% and 126.40% at 873 K and 60 s, respectively, which suggests PVA can be completely gasified in SCW. The results indicate supercritical water gasification for hydrogen generation is a promising process for the treatment of PVA wastewater.

  2. Efficiency Evaluation of a Photovoltaic System Simultaneously Generating Solar Electricity and Hydrogen for Energy Storage

    Directory of Open Access Journals (Sweden)

    Abermann S.

    2012-10-01

    Full Text Available The direct combination of a photovoltaic system with an energy storage component appears desirable since it produces and stores electrical energy simultaneously, enabling it to compensate power generation fluctuations and supply sufficient energy during low- or non-irradiation periods. A novel concept based on hydrogenated amorphous silicon (a-Si:H triple-junction solar cells, as for example a-Si:H/a-SiGe:H/a-SiGe:H, and a solar water splitting system integrating a polymer electrolyte membrane (PEM electrolyser is presented. The thin film layer-by-layer concept allows large-area module fabrication applicable to buildings, and exhibits strong cost-reduction potential as compared to similar concepts. The evaluation shows that it is possible to achieve a sufficient voltage of greater than 1.5 V for effective water splitting with the a-Si based solar cell. Nevertheless, in the case of grid-connection, the actual energy production cost for hydrogen storage by the proposed system is currently too high.

  3. Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Christopher [Univ. of California, Berkeley, CA (United States)

    2014-05-15

    Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

  4. Generation of hydrogen peroxide from San Joaquin Valley particles in a cell-free solution

    Science.gov (United States)

    Shen, H.; Barakat, A. I.; Anastasio, C.

    2011-01-01

    Epidemiological studies have shown a correlation between exposure to ambient particulate matter (PM) and adverse health effects. One proposed mechanism of PM-mediated health effects is the generation of reactive oxygen species (ROS) - e.g., superoxide (•O2-), hydrogen peroxide (HOOH), and hydroxyl radical (•OH) - followed by oxidative stress. There are very few quantitative, specific measures of individual ROS generated from PM, but this information would help to more quantitatively address the link between ROS and the health effects of PM. To address this gap, we quantified the generation of HOOH by PM collected at an urban (Fresno) and rural (Westside) site in the San Joaquin Valley (SJV) of California during summer and winter from 2006 to 2009. HOOH was quantified by HPLC after extracting the PM in a cell-free, phosphate-buffered saline (PBS) solution with or without 50 μM ascorbate (Asc). Our results show that the urban PM generally generates much more HOOH than the rural PM but that there is no apparent seasonal difference in HOOH generation. In nearly all of the samples the addition of a physiologically relevant concentration of Asc greatly enhances HOOH formation, but a few of the coarse PM samples were able to generate a considerable amount of HOOH in the absence of added Asc, indicating the presence of unknown reductants. Normalized by air volume, the fine PM (PM2.5) generally makes more HOOH than the corresponding coarse PM (PMcf, i.e., 2.5 to 10 μm), primarily because the mass concentration of PM2.5 is much higher than that of PMcf. However, normalized by PM mass, the coarse PM typically generates more HOOH than the fine PM. The amount of HOOH produced by SJV PM is reduced on average by (78 ± 15)% when the transition metal chelator desferoxamine (DSF) is added to the extraction solution, indicating that transition metals play a dominant role in HOOH generation. By measuring calibration curves of HOOH generation from copper, and quantifying copper

  5. Generation of hydrogen peroxide from San Joaquin Valley particles in a cell-free solution

    Directory of Open Access Journals (Sweden)

    H. Shen

    2010-09-01

    Full Text Available Epidemiological studies have shown a correlation between exposure to ambient particulate matter (PM and adverse health effects. One proposed mechanism of PM-mediated health effects is the generation of reactive oxygen species (ROS – e.g., superoxide (•O2, hydrogen peroxide (HOOH, and hydroxyl radical (•OH – followed by oxidative stress. There are very few quantitative, specific measures of individual ROS generated from PM, but this information would help to more quantitatively address the link between ROS and the health effects of PM. To address this gap, we quantified the generation of HOOH by PM collected at an urban (Fresno and rural (Westside site in the San Joaquin Valley (SJV of California during summer and winter from 2006 to 2009. HOOH was quantified by HPLC after extracting the PM in a cell-free, phosphate-buffered saline (PBS solution with or without 50 μM ascorbate (Asc. Our results show that the urban PM generally generates much more HOOH than the rural PM but that there is no apparent seasonal difference in HOOH generation. In nearly all of the samples the addition of a physiologically relevant concentration of Asc greatly enhances HOOH formation, but a few of the coarse PM samples were able to generate a considerable amount of HOOH in the absence of added Asc, indicating the presence of unknown reductants. Normalized by air volume, the fine PM (PM2.5 generally makes more HOOH than the corresponding coarse PM (PMcf, i.e., 2.5 to 10 μm, primarily because the mass concentration of PM2.5 is much higher than that of PMcf. However, normalized by PM mass, the coarse PM typically generates more HOOH than the fine PM. The amount of HOOH produced by SJV PM is reduced on average by (78±15% when the transition metal chelator desferoxamine (DSF is added to the extraction solution, indicating that transition metals play a dominant role in HOOH generation. By

  6. Generation of hydrogen peroxide from San Joaquin Valley particles in a cell-free solution

    Directory of Open Access Journals (Sweden)

    H. Shen

    2011-01-01

    Full Text Available Epidemiological studies have shown a correlation between exposure to ambient particulate matter (PM and adverse health effects. One proposed mechanism of PM-mediated health effects is the generation of reactive oxygen species (ROS – e.g., superoxide (O2, hydrogen peroxide (HOOH, and hydroxyl radical (OH – followed by oxidative stress. There are very few quantitative, specific measures of individual ROS generated from PM, but this information would help to more quantitatively address the link between ROS and the health effects of PM. To address this gap, we quantified the generation of HOOH by PM collected at an urban (Fresno and rural (Westside site in the San Joaquin Valley (SJV of California during summer and winter from 2006 to 2009. HOOH was quantified by HPLC after extracting the PM in a cell-free, phosphate-buffered saline (PBS solution with or without 50 μM ascorbate (Asc. Our results show that the urban PM generally generates much more HOOH than the rural PM but that there is no apparent seasonal difference in HOOH generation. In nearly all of the samples the addition of a physiologically relevant concentration of Asc greatly enhances HOOH formation, but a few of the coarse PM samples were able to generate a considerable amount of HOOH in the absence of added Asc, indicating the presence of unknown reductants. Normalized by air volume, the fine PM (PM2.5 generally makes more HOOH than the corresponding coarse PM (PMcf, i.e., 2.5 to 10 μm, primarily because the mass concentration of PM2.5 is much higher than that of PMcf. However, normalized by PM mass, the coarse PM typically generates more HOOH than the fine PM. The amount of HOOH produced by SJV PM is reduced on average by (78 ± 15% when the transition metal chelator desferoxamine (DSF is added to the extraction solution, indicating that transition metals play a dominant role in HOOH

  7. Acoustically induced optical second harmonic generation in hydrogenated amorphous silicon films

    CERN Document Server

    Ebothe, J; Cabarrocas, P R I; Godet, C; Equer, B

    2003-01-01

    Acoustically induced second harmonic generation (AISHG) in hydrogenated amorphous silicon (a-Si : H) films of different morphology has been observed. We have found that with increasing acoustical power, the optical SHG of Gd : YAB laser light (lambda = 2.03 mu m) increases and reaches its maximum value at an acoustical power density of about 2.10 W cm sup - sup 2. With decreasing temperature, the AISHG signal strongly increases below 48 K and correlates well with the temperature behaviour of differential scanning calorimetry indicating near-surface temperature phase transition. The AISHG maxima were observed at acoustical frequencies of 10-11, 14-16, 20-22 and 23-26 kHz. The independently performed measurements of the acoustically induced IR spectra have shown that the origin of the observed phenomenon is the acoustically induced electron-phonon anharmonicity in samples of different morphology.

  8. Cytochrome c catalyzes the in vitro synthesis of arachidonoyl glycine

    International Nuclear Information System (INIS)

    Long chain fatty acyl glycines are an emerging class of biologically active molecules that occur naturally and produce a wide array of physiological effects. Their biosynthetic pathway, however, remains unknown. Here we report that cytochrome c catalyzes the synthesis of N-arachidonoyl glycine (NAGly) from arachidonoyl coenzyme A and glycine in the presence of hydrogen peroxide. The identity of the NAGly product was verified by isotope labeling and mass analysis. Other heme-containing proteins, hemoglobin and myoglobin, were considerably less effective in generating arachidonoyl glycine as compared to cytochrome c. The reaction catalyzed by cytochrome c in vitro points to its potential role in the formation of NAGly and other long chain fatty acyl glycines in vivo

  9. Redirection of metabolism for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Harwood, Caroline S.

    2011-11-28

    This project is to develop and apply techniques in metabolic engineering to improve the biocatalytic potential of the bacterium Rhodopseudomonas palustris for nitrogenase-catalyzed hydrogen gas production. R. palustris, is an ideal platform to develop as a biocatalyst for hydrogen gas production because it is an extremely versatile microbe that produces copious amounts of hydrogen by drawing on abundant natural resources of sunlight and biomass. Anoxygenic photosynthetic bacteria, such as R. palustris, generate hydrogen and ammonia during a process known as biological nitrogen fixation. This reaction is catalyzed by the enzyme nitrogenase and normally consumes nitrogen gas, ATP and electrons. The applied use of nitrogenase for hydrogen production is attractive because hydrogen is an obligatory product of this enzyme and is formed as the only product when nitrogen gas is not supplied. Our challenge is to understand the systems biology of R. palustris sufficiently well to be able to engineer cells to produce hydrogen continuously, as fast as possible and with as high a conversion efficiency as possible of light and electron donating substrates. For many experiments we started with a strain of R. palustris that produces hydrogen constitutively under all growth conditions. We then identified metabolic pathways and enzymes important for removal of electrons from electron-donating organic compounds and for their delivery to nitrogenase in whole R. palustris cells. For this we developed and applied improved techniques in 13C metabolic flux analysis. We identified reactions that are important for generating electrons for nitrogenase and that are yield-limiting for hydrogen production. We then increased hydrogen production by blocking alternative electron-utilizing metabolic pathways by mutagenesis. In addition we found that use of non-growing cells as biocatalysts for hydrogen gas production is an attractive option, because cells divert all resources away from growth and

  10. Evaluation Of Methods To Measure Hydrogen Generation Rate In A Shielded Cell Environment And A Method Recommendation

    Energy Technology Data Exchange (ETDEWEB)

    Stone, M. E.

    2012-11-07

    The purpose of this document is to describe the current state of the art for determination of hydrogen generation rates of radioactive slurries and solutions to provide a basis for design, fabrication, testing, and implementation of a measurement method for Hydrogen Generation Rate (HGR) during qualification of waste feeds for the Hanford Waste Treatment and Immobilization Plant (WTP). The HGR measurement will be performed on samples of the Low Activity Waste (LAW) and High Level Waste (HLW) staged waste feeds for the WTP as well as on samples from selected unit operations testing during the qualification program. SRNL has performed a review of techniques utilized to measure HGR of high level radioactive waste slurries, evaluated the Hanford 222-S Laboratory method for measurement of hydrogen, and reviewed the hydrogen generation rate models for Hanford waste.Based on the literature review, method evaluation, and SRNL experience with measuring hydrogen generation rate, SRNL recommends that a continuous flow system with online gas analysis be used as the HGR measurement method during waste qualification.

  11. Iodine-catalyzed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, J.T.; Duffield, J.E.; Davidson, M.G. (Amoco Oil Company, Naperville, IL (USA). Research and Development Dept.)

    Coals of two different ranks were liquefied in high yields using catalytic quantities of elemental iodine or iodine compounds. Iodine monochloride was found to be especially effective for enhancing both coal conversion and product quality. It appears that enhancement in coal conversion is due to the unique ability of iodine to catalyze radical-induced bond scission and hydrogen addition to the coal macromolecule or coal-derived free radicals. The starting iodine can be fully accounted for in the reaction products as both organic-bound and water-soluble forms. Unconverted coal and the heavy product fractions contain the majority of the organic-bound iodine. The results of iodine-catalyzed coal reactions emphasize the need for efficient hydrogen atom transfer along with bond scission to achieve high conversion and product quality. 22 refs., 12 tabs.

  12. Hydrogen generation in CSP plants and maintenance of DPO/BP heat transfer fluids - A simulation approach

    Science.gov (United States)

    Kuckelkorn, Thomas; Jung, Christian; Gnädig, Tim; Lang, Christoph; Schall, Christina

    2016-05-01

    The ageing of diphenyl oxide/ biphenyl (DPO/BP) Heat Transfer Fluids (HTFs) implies challenging tasks for operators of parabolic trough power plants in order to find the economic optimum between plant performance and O&M costs. Focusing on the generation of hydrogen, which is effecting from the HTF ageing process, the balance of hydrogen pressure in the HTF is simulated for different operation scenarios. Accelerated build-up of hydrogen pressure in the HTF is causing increased permeation into the annular vacuum space of the installed receivers and must be avoided in order to maintain the performance of these components. Therefore, the effective hydrogen partial pressure in the HTF has to be controlled and limited according to the specified values so that the vacuum lifetime of the receivers and the overall plant performance can be ensured. In order to simulate and visualize the hydrogen balance of a typical parabolic trough plant, initially a simple model is used to calculate the balance of hydrogen in the system and this is described. As input data for the simulation, extrapolated hydrogen generation rates have been used, which were calculated from results of lab tests performed by DLR in Cologne, Germany. Hourly weather data, surface temperatures of the tubing system calculated by using the simulation tool from NREL, and hydrogen permeation rates for stainless steel and carbon steel grades taken from literature have been added to the model. In a first step the effect of HTF ageing, build-up of hydrogen pressure in the HTF and hydrogen loss rates through piping and receiver components have been modeled. In a second step a selective hydrogen removal process has been added to the model. The simulation results are confirming the need of active monitoring and controlling the effective hydrogen partial pressure in parabolic trough solar thermal power plants with DPO/BP HTF. Following the results of the simulation, the expected plant performance can only be achieved

  13. Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube

    International Nuclear Information System (INIS)

    Hydrogen was generated from ammonia borane complex by hydrolysis using cobalt nanocluster catalyst supported on polydopamine functionalized MWCNTs (multi-walled carbon nanotubes). The impregnation-chemical reduction method was used for the preparation of the supported catalyst. The nanocluster catalyst support was formed by in-situ oxidative polymerization of dopamine on the MWCNTs in alkaline solution at room temperature. The structural and physical–chemical properties of the nanocluster catalyst were characterized by FT-IR (Fourier transform infrared spectroscopy), EDX (energy-dispersive X-ray spectroscopy), SEM (scanning electron microscope), XRD (X-ray diffraction) and TEM (transmission electron microscopy). The nanocluster catalyst showed good catalytic activity for the hydrogen generation from aqueous ammonia borane complex. A reusability test to determine the practical usage of the catalyst was also investigated. The result revealed that the catalyst maintained an appreciable catalytic performance and stability in terms of its reusability after three cycle of reuse for the hydrolysis reaction. Also, the activation energy for the hydrolysis of ammonia borane complex was estimated to be 50.41 kJmol−1, which is lower than the values of some of the reported catalyst. The catalyst can be considered as a promising candidate in developing highly efficient portable hydrogen generation systems such as PEMFC (proton exchange membrane fuel cells). - Highlights: • Co/Pdop-o-MWCNT (Pdop functionalized MWCNT supported cobalt nanocluster) catalyst was synthesized for hydrogen generation. • It is an active catalyst for hydrogen generation via hydrolysis of ammonia borane. • It showed good stability in terms of reusability for the hydrogen generation

  14. Effect of ball-milling duration and dehydrogenation on the morphology, microstructure and catalyst dispersion in Ni-catalyzed MgH2 hydrogen storage materials

    International Nuclear Information System (INIS)

    The effects of high-energy ball-milling on catalyst morphology and dispersion as a function of milling duration and on hydrogen desorption were investigated. Samples of MgH2 doped with 0.05 Ni catalyst were examined after 1, 5 and 10 h of milling. Longer milling durations produced finer catalyst particle sizes and more uniform dispersions, but yielded higher hydrogen desorption temperatures. This behavior is attributed to the formation of Mg2NiH4 with increased milling times. Electron tomography was used to show that the Ni particles reside both inside and outside the MgH2 particles. On dehydrogenation there was a redistribution of catalyst and continued formation of Mg2Ni. The formation of this phase is proposed to explain the reported degradation of hydrogen capacity and the change in kinetics of this system with cycling

  15. Sliding discharges in steam: effects of dielectric surface and hydrocarbon additives on hydrogen, oxygen and hydrogen peroxide generation

    International Nuclear Information System (INIS)

    A sliding surface discharge was formed on a dielectric layer in steam at ∼100 °C and atmospheric pressure. The material properties and the thickness of the dielectric layer were found to strongly affect the energy deposition into the plasma. With a 0.32 cm thick dielectric the energy deposition was 1.4 times greater than with a 0.48 cm thick dielectric, and with window glass it was 1.3 times greater than with Macor of the same thickness. Product gases were H2 (73 ± 4%) and O2 (27 ± 1%), and H2O2 accumulated in the condensed water up to 0.4 g l−1. The energy yield for hydrogen was 1.2 ± 0.1 g H2 kWh−1 and independent of the input power and thickness or material of the dielectric. However, for hydrogen peroxide the energy yield, which varied between 0.61 and 3.2 g H2O2 kWh−1, was found to depend strongly on the thickness and material of the dielectric. The addition of benzene to the steam increased the energy efficiency of hydrogen to 2.3 g kWh−1, and decreased oxygen and hydrogen peroxide by about 3 and 6 times, respectively. It also caused the deposition of phenol and polymer-like layers on the dielectric. The results are explained on the basis of reactions of H and OH radicals adsorbed on the surface and/or in gas phase. (paper)

  16. Vanadium Hydrogen Sulfate Catalyzed Solvent-Free Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and Bis-(indolyl) methanes

    International Nuclear Information System (INIS)

    We have developed a mild, simple and efficient method for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones and bis-(indolyl) methanes catalyzed by V(HSO4)3. Based on our studies, this method offers several adavantages including mild reaction conditions, good to high yields of the products, short reaction times, solvent-free reaction conditions and simple experimental procedure. 3,4-Dihydropyrimidin-2(1H)-ones and their derivatives have attracted increasing interest due to their wide range of therapeutical and pharmacological properties, such as antiviral, antitumor, antibacterial, and antiinflammatory properties. Some of them have been successfully used as calcium channel blockers, antihypertensive agents, and α1a-antagonists. Moreover, several marine alkaloids whose molecular structures contain the dihydropyrimidinone core also exhibit interesting biological activities. Therefore, synthesis of these type of compounds is still of great importance

  17. Modulation of Na+/K+ ATPase Activity by Hydrogen Peroxide Generated through Heme in L. amazonensis.

    Directory of Open Access Journals (Sweden)

    Nathália Rocco-Machado

    Full Text Available Leishmania amazonensis is a protozoan parasite that occurs in many areas of Brazil and causes skin lesions. Using this parasite, our group showed the activation of Na+/K+ ATPase through a signaling cascade that involves the presence of heme and protein kinase C (PKC activity. Heme is an important biomolecule that has pro-oxidant activity and signaling capacity. Reactive oxygen species (ROS can act as second messengers, which are required in various signaling cascades. Our goal in this work is to investigate the role of hydrogen peroxide (H2O2 generated in the presence of heme in the Na+/K+ ATPase activity of L. amazonensis. Our results show that increasing concentrations of heme stimulates the production of H2O2 in a dose-dependent manner until a concentration of 2.5 μM heme. To confirm that the effect of heme on the Na+/K+ ATPase is through the generation of H2O2, we measured enzyme activity using increasing concentrations of H2O2 and, as expected, the activity increased in a dose-dependent manner until a concentration of 0.1 μM H2O2. To investigate the role of PKC in this signaling pathway, we observed the production of H2O2 in the presence of its activator phorbol 12-myristate 13-acetate (PMA and its inhibitor calphostin C. Both showed no effect on the generation of H2O2. Furthermore, we found that PKC activity is increased in the presence of H2O2, and that in the presence of calphostin C, H2O2 is unable to activate the Na+/K+ ATPase. 100 μM of Mito-TEMPO was capable of abolishing the stimulatory effect of heme on Na+/K+ ATPase activity, indicating that mitochondria might be the source of the hydrogen peroxide production induced by heme. The modulation of L. amazonensis Na+/K+ ATPase by H2O2 opens new possibilities for understanding the signaling pathways of this parasite.

  18. Modulation of Na+/K+ ATPase Activity by Hydrogen Peroxide Generated through Heme in L. amazonensis.

    Science.gov (United States)

    Rocco-Machado, Nathália; Cosentino-Gomes, Daniela; Meyer-Fernandes, José Roberto

    2015-01-01

    Leishmania amazonensis is a protozoan parasite that occurs in many areas of Brazil and causes skin lesions. Using this parasite, our group showed the activation of Na+/K+ ATPase through a signaling cascade that involves the presence of heme and protein kinase C (PKC) activity. Heme is an important biomolecule that has pro-oxidant activity and signaling capacity. Reactive oxygen species (ROS) can act as second messengers, which are required in various signaling cascades. Our goal in this work is to investigate the role of hydrogen peroxide (H2O2) generated in the presence of heme in the Na+/K+ ATPase activity of L. amazonensis. Our results show that increasing concentrations of heme stimulates the production of H2O2 in a dose-dependent manner until a concentration of 2.5 μM heme. To confirm that the effect of heme on the Na+/K+ ATPase is through the generation of H2O2, we measured enzyme activity using increasing concentrations of H2O2 and, as expected, the activity increased in a dose-dependent manner until a concentration of 0.1 μM H2O2. To investigate the role of PKC in this signaling pathway, we observed the production of H2O2 in the presence of its activator phorbol 12-myristate 13-acetate (PMA) and its inhibitor calphostin C. Both showed no effect on the generation of H2O2. Furthermore, we found that PKC activity is increased in the presence of H2O2, and that in the presence of calphostin C, H2O2 is unable to activate the Na+/K+ ATPase. 100 μM of Mito-TEMPO was capable of abolishing the stimulatory effect of heme on Na+/K+ ATPase activity, indicating that mitochondria might be the source of the hydrogen peroxide production induced by heme. The modulation of L. amazonensis Na+/K+ ATPase by H2O2 opens new possibilities for understanding the signaling pathways of this parasite. PMID:26070143

  19. Modelling studies to proper size a hydrogen generator for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Maggio, G.; Recupero, V.; Di Leonardo, R.; Lagana, M. [Istituto CNR-TAE, Lucia, Messina (Italy)

    1996-12-31

    Based upon an extensive survey of literature a mathematical model has been developed to study the temperature profile along the catalytic bed of a reactor for the methane partial oxidation. The model allowed a preliminary design of a 5 Nm{sup 3} syngas/h prototype to be integrated with second generation fuel cells as hydrogen generator (in the framework of the EC-JOU2 contract). This design was based on some target features, including the choice of a GHSV (gas hour space velocity) equal to 80000 h{sup -1}, a catalyst particle size of 1/8inches, a molar air/methane ratio of 2.7 (i.e. O{sub 2}/CH{sub 4}=0.53), a linear velocity in the catalytic bed of about 2 m/sec, and an inert/catalyst ratio 3:1. Starting from this data, the work has been concerned with the identification of the controlling regime (kinetic or diffusional), and then with the estimation of the gas composition and temperature profiles along the reactor. A comparison between experimental and model results has also been accomplished.

  20. Generation of Hydrogen, Lignin and Sodium Hydroxide from Pulping Black Liquor by Electrolysis

    Directory of Open Access Journals (Sweden)

    Guangzai Nong

    2015-12-01

    Full Text Available Black liquor is generated in Kraft pulping of wood or non-wood raw material in pulp mills, and regarded as a renewable resource. The objective of this paper was to develop an effective means to remove the water pollutants by recovery of both lignin and sodium hydroxide from black liquor, based on electrolysis. The treatment of a 1000 mL of black liquor (122 g/L solid contents consumed 345.6 kJ of electric energy, and led to the generation of 30.7 g of sodium hydroxide, 0.82 g of hydrogen gas and 52.1 g of biomass solids. Therefore, the recovery ratios of elemental sodium and biomass solids are 80.4% and 76%, respectively. Treating black liquor by electrolysis is an environmentally friendly technology that can, in particular, be an alternative process in addressing the environmental issues of pulping waste liquor to the small-scale mills without black liquor recovery.

  1. Ion acceleration enhancement in laser-generated plasmas by metallic doped hydrogenated polymers

    Directory of Open Access Journals (Sweden)

    Angela Maria Mezzasalma

    2009-05-01

    Full Text Available Laser-generated plasmas in vacuum were obtained by ablating hydrogenated polymers at the Physics Department of the University of Messina and at the PALS Laboratory in Prague. In the first case a 3 ns,532 nm Nd:Yag laser, at 1010 W/cm2 intensity was employed.In the second case a 300 ps, 438 nm iodine laser, at 5x1014W/cm2 intensity was employed. Different ion collectors were usedin a time-of-flight configuration to monitor the ejected ions from theplasma at different angles with respect to the direction normal tothe target surface. Measurements demonstrated that the mean ionvelocity, directed orthogonally to the target surface, increases forablation of polymers doped with metallic elements with respect tothe nondoped one. The possible mechanism explaining theresults can be found in the different electron density of theplasma, due to the higher number of electrons coming from the dopingelements. This charge enhancement increases the equivalent ionvoltage acceleration, i.e. the electric field generated in the non-equilibrium plasma placed in front of the ablated target surface.

  2. Carbon Monoxide-induced Stomatal Closure Involves Generation of Hydrogen Peroxide in Vicia faba Guard Cells

    Institute of Scientific and Technical Information of China (English)

    Xiao-Ping She; Xi-Gui Song

    2008-01-01

    Here the regulatory role of CO during stomatal movement In Vicla faba L. was surveyed. Results Indicated that, like hydrogen peroxide (H2O2), CO donor Hematin induced stomatal closure in dose- and time-dependent manners. These responses were also proven by the addition of gaseous CO aqueous solution with different concentrations, showing the first time that CO and H2O2 exhibit the similar regulation role in the atomatal movement. Moreover, our data showed that ascorbic acid (ASA, an important reducing substrate for H2O2 removal) and diphenylene iodonium (DPI, an inhibitor of the H2O2-generating enzyme NADPH oxidase) not only reversed stomatal closure by CO, but also suppressed the H2O2 fluorescence induced by CO, implying that CO induced-atomatal closure probably involves H2O2 signal. Additionally, the CO/NO scavenger hemoglobin (Hb) and CO specific synthetic inhibitor ZnPPIX, ASA and DPI reversed the darkness-induced stomatal closure and H2O2 fluorescence. These results show that, perhaps like H2O2, the levels of CO in guard cells of V. faba are higher In the dark than in light, HO-1 and NADPH oxidase are the enzyme systems responsible for generating endogenous CO and H2O2 in darkness respectively, and that CO is involved in darkness-induced H2O2 synthesis in V. faba guard cells.

  3. Synergistic effects in hydrogen production through water sonophotolysis catalyzed by new La{sub 2x}Ga{sub 2y}In{sub 2(1-x-y)}O{sub 3} solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gentili, Pier Luigi; Ortica, Fausto; Elisei, Fausto [Dipartimento di Chimica, Universita di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); CIRIAF, Via G. Duranti 67, 06125 Perugia (Italy); Penconi, Marta [Dipartimento di Chimica, Universita di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); Cotana, Franco; Rossi, Federico [CIRIAF, Via G. Duranti 67, 06125 Perugia (Italy)

    2009-11-15

    This work presents experimental data regarding hydrogen production by heterogeneous photocatalysis, sonocatalysis and sonophotocatalysis in water/ethanol solutions. Three new metal oxides solid solutions, LaGa{sub 0.5}In{sub 0.5}O{sub 3}, La{sub 0.8}Ga{sub 0.2}InO{sub 3} and S-doped La{sub 0.8}Ga{sub 0.2}InO{sub 3} (S:La{sub 0.8}Ga{sub 0.2}InO{sub 3}), have been synthesized and used as catalysts. Their action has been tested in diluted and concentrated suspensions wherein the content of ethanol, acting as sacrificial reagent, has been fixed to 10% in volume. The largest amounts of hydrogen have, always, been achieved from concentrated suspensions and by using S:La{sub 0.8}Ga{sub 0.2}InO{sub 3} as catalyst. Ultrasounds, generated by 38 kHz and 50 W piezoelectric transducer, were more effective than light coming from a 35 W Xe lamp. Moreover, the hybrid action of light and ultrasounds determined a remarkable synergistic effect on the hydrogen production. Therefore, sonophotocatalysis is a promising way of generating hydrogen from water/ethanol solutions. In the near future, a net hydrogen production is expected to be achieved by improving the proposed process efficiencies. (author)

  4. Investigation of advanced nanostructured multijunction photoanodes for enhanced solar hydrogen generation via water splitting

    Science.gov (United States)

    Ishihara, Hidetaka

    As the worldwide demand for fossil-based fuel increases every day and the fossil reserve continues to be depleted, the need for alternative/renewable energy sources has gained momentum. Electric, hybrid, and hydrogen cars have been at the center of discussion lately among consumers, automobile manufacturers, and politicians, alike. The development of a fuel-cell based engine using hydrogen has been an ambitious research area over the last few decades-ever since Fujishima showed that hydrogen can be generated via the solar-energy driven photo-electrolytic splitting of water. Such solar cells are known as Photo-Electro-Chemical (PEC) solar cells. In order to commercialize this technology, various challenges associated with photo-conversion efficiency, chemical corrosion resistance, and longevity need to be overcome. In general, metal oxide semiconductors such as titanium dioxide (TiO 2, titania) are excellent candidates for PEC solar cells. Titania nanotubes have several advantages, including biocompatibility and higher chemical stability. Nevertheless, they can absorb only 5-7% of the solar spectrum which makes it difficult to achieve the higher photo-conversion efficiency required for successful commercial applications. A two-prong approach was employed to enhance photo-conversion efficiency: 1) surface modification of titania nanotubes using plasma treatment and 2) nano-capping of the titania nanotubes using titanium disilicide. The plasma surface treatment with N2 was found to improve the photo-current efficiency of titania nanotubes by 55%. Similarly, a facile, novel approach of nano-capping titania nanotubes to enhance their photocurrent response was also investigated. Electrochemically anodized titania nanotubes were capped by coating a 25 nm layer of titanium disilicide using RF magnetron sputtering technique. The optical properties of titania nanotubes were not found to change due to the capping; however, a considerable increase (40%) in the photocurrent

  5. Study of the acceleration of ammonia generation process from poultry residues aiming at hydrogen production

    International Nuclear Information System (INIS)

    environment. The possibility of ammonia emission increment observed in this study, and its use in a system of ammonia generation - hydrogen production - fuel cell might produce electricity in the enterprise, reducing the expenses of the farms and providing a properly destination for these residues. (author)

  6. Hydrogen system (hydrogen fuels feasibility)

    International Nuclear Information System (INIS)

    This feasibility study on the production and use of hydrogen fuels for industry and domestic purposes includes the following aspects: physical and chemical properties of hydrogen; production methods steam reforming of natural gas, hydrolysis of water; liquid and gaseous hydrogen transportation and storage (hydrogen-hydride technology); environmental impacts, safety and economics of hydrogen fuel cells for power generation and hydrogen automotive fuels; relevant international research programs

  7. Generation of core–shell nanoparticles Al@Ti by laser ablation in liquid for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Serkov, A.A. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov street, 119991 Moscow (Russian Federation); The Federal State Educational Institution of Higher Professional Education, “Moscow Institute of Physics and Technology (State University)”, 9, Institutsky lane, 141700, Dolgoprudny, Moscow (Russian Federation); Barmina, E.V.; Simakin, A.V. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov street, 119991 Moscow (Russian Federation); Kuzmin, P.G., E-mail: qzzzma@gmail.com [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov street, 119991 Moscow (Russian Federation); Voronov, V.V. [A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov street, 119991 Moscow (Russian Federation); Shafeev, G.A. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38, Vavilov street, 119991 Moscow (Russian Federation); National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), 31, Kashirskoye highway, 115409 Moscow (Russian Federation)

    2015-09-01

    Highlights: • Core–shell Al@Ti NPs are generated by laser ablation in isopropanol. • Isopropanol was saturated with molecular hydrogen. • The composite metallic Al-Ti target was used. • HR TEM characterization shows that Ti core is covered by epitaxial Al shell. • Al@Ti NPs are promising for hydrogen storage. - Abstract: Core–shell Al@Ti nanoparticles are generated by ablation of a composite Ti–Al target in liquid isopropanol saturated with molecular hydrogen using a Nd:YAG laser with pulse duration of 10 ps and repetition rate of 200 kHz. The target is made of two plates of corresponding metals stacked together and placed into a flowing cell reactor. Transmission Electron Microscopy analysis of generated NPs reveals their core–shell structure with Ti core and Al shell. Average size of NPs determined by means of measuring disk centrifuge is around 40 nm. Saturation of NPs by hydrogen is due to sharp dependence of its solubility in these metals on temperature. XRD studies of generated NPs show the peaks of both metallic Ti and Al with some amount of TiO{sub 2}. No peaks of Ti–Al alloys are observed.

  8. Fractal disperse hydrogen sorption kinetics in spark discharge generated Mg/NbOx and Mg/Pd nanocomposites

    NARCIS (Netherlands)

    Anastasopol, A.; Pfeiffer, T.V.; Schmidt-Ott, A.; Mulder, F.M.; Eijt, S.W.H.

    2011-01-01

    Isothermal hydrogen desorption of spark discharge generated Mg/NbOx and Mg/Pd metal hydride nanocomposites is consistently described by a kinetic model based on multiple reaction rates, in contrast to the Johnson-Mehl-Avrami-Kolmogorov [M. Avrami, J. Phys. Chem. 9, 177 (1941); W. A. Johnson and R. F

  9. Generation of core–shell nanoparticles Al@Ti by laser ablation in liquid for hydrogen storage

    International Nuclear Information System (INIS)

    Highlights: • Core–shell Al@Ti NPs are generated by laser ablation in isopropanol. • Isopropanol was saturated with molecular hydrogen. • The composite metallic Al-Ti target was used. • HR TEM characterization shows that Ti core is covered by epitaxial Al shell. • Al@Ti NPs are promising for hydrogen storage. - Abstract: Core–shell Al@Ti nanoparticles are generated by ablation of a composite Ti–Al target in liquid isopropanol saturated with molecular hydrogen using a Nd:YAG laser with pulse duration of 10 ps and repetition rate of 200 kHz. The target is made of two plates of corresponding metals stacked together and placed into a flowing cell reactor. Transmission Electron Microscopy analysis of generated NPs reveals their core–shell structure with Ti core and Al shell. Average size of NPs determined by means of measuring disk centrifuge is around 40 nm. Saturation of NPs by hydrogen is due to sharp dependence of its solubility in these metals on temperature. XRD studies of generated NPs show the peaks of both metallic Ti and Al with some amount of TiO2. No peaks of Ti–Al alloys are observed

  10. Thermodynamic analysis of SCW NPP cycles with thermo-chemical co-generation of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Naidin, N.; Mokry, S.; Monichan, R.; Chophla, K.; Pioro, I. [Faculty of Energy Systems and Nuclear Science, Univ. of Ontario Inst. of Technology, Oshawa, Ontario (Canada)], E-mail: Maria.Naidin@mycampus.uoit.ca, Sarah.Mokry@mycampus.uoit.ca, Romson.Monichan@uoit.ca, Karan.Chophla@mycampus.uoit.ca, Igor.Pioro@uoit.ca; Naterer, G.; Gabriel, K. [Faculty of Engineering and Applied Science, Univ. of Ontario Inst. of Technology, Oshawa, Ontario (Canada)], E-mail: Greg.Naterer@uoit.ca, Kamiel.Gabriel@uoit.ca

    2009-07-01

    Research activities are currently conducted worldwide to develop Generation IV nuclear reactor concepts with the objective of improving thermal efficiency and increasing economic competitiveness of Generation IV Nuclear Power Plants (NPPs) compared to modern thermal power plants. The Super-Critical Water-cooled Reactor (SCWR) concept is one of the six Generation IV options chosen for further investigation and development in several countries including Canada and Russia. Water-cooled reactors operating at subcritical pressures (10 - 16 MPa) have provided a significant amount of electricity production for the past 50 years. However, the thermal efficiency of the current NPPs is not very high (30 - 35%). As such, more competitive designs, with higher thermal efficiencies, which will be close to that of modern thermal power plants (45 - 50%), need to be developed and implemented. Super-Critical Water (SCW) NPPs will have much higher operating parameters compared to current NPPs (i.e., steam pressures of about 25 MPa and steam outlet temperatures up to 625{sup o}C). Furthermore, SCWRs operating at higher temperatures can facilitate an economical co-generation of hydrogen through thermochemical cycles (particularly, the copper-chlorine cycle) or direct high-temperature electrolysis. The two SCW NPP cycles proposed by this paper are based on direct, regenerative, no-reheat and single-reheat configurations. As such, the main parameters and performance in terms of thermal efficiency of the SCW NPP concepts mentioned above are being analyzed. The cycles are generally comprised of: an SCWR, a SC turbine, one deaerator, ten feedwater heaters, and pumps. The SC turbine of the no-reheat cycle consists of one High-Pressure (HP) cylinder and two Low-Pressure (LP) cylinders. Alternatively, the SC turbine for the single-reheat cycle is comprised of one High-Pressure (HP) cylinder, one Intermediate-Pressure (IP) cylinder and two Low-Pressure (LP) cylinders. Since the single

  11. Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

    Directory of Open Access Journals (Sweden)

    Michael M. Bobek

    2012-10-01

    Full Text Available A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM and electron dispersive X-ray spectroscopy (EDS, the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

  12. Minimum Entropy Generation Theorem Investigation and Optimization of Metal Hydride Alloy Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Chi-Chang Wang

    2014-05-01

    Full Text Available The main purpose of this paper is to carry out numerical simulation of the hydrogen storage on exothermic reaction of metal hydride LaNi5 alloy container. In addition to accelerating the reaction speed of the internal metal hydride by internal control tube water-cooled mode, analyze via the application of second law of thermodynamics the principle of entropy generation. Use COMSOL Mutilphysics 4.3 a to engage in finite element method value simulation on two-dimensional axisymmetric model. Also on the premise that the internal control tube parameters the radius ri, the flow rate U meet the metal hydride saturation time, observe the reaction process of two parameters on the tank, entropy distribution and the results of the accumulated entropy. And try to find the internal tube parameter values of the minimum entropy, whose purpose is to be able to identify the reaction process and the reaction results of internal tank’s optimum energy conservation.

  13. RADIOLYTIC HYDROGEN GENERATION INSAVANNAH RIVER SITE (SRS) HIGH LEVEL WASTETANKS COMPARISON OF SRS AND HANFORDMODELING PREDICTIONS

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, C; Ned Bibler, N

    2009-04-15

    In the high level waste tanks at the Savannah River Site (SRS), hydrogen is produced continuously by interaction of the radiation in the tank with water in the waste. Consequently, the vapor spaces of the tanks are purged to prevent the accumulation of H{sub 2} and possible formation of a flammable mixture in a tank. Personnel at SRS have developed an empirical model to predict the rate of H{sub 2} formation in a tank. The basis of this model is the prediction of the G value for H{sub 2} production. This G value is the number of H{sub 2} molecules produced per 100 eV of radiolytic energy absorbed by the waste. Based on experimental studies it was found that the G value for H{sub 2} production from beta radiation and from gamma radiation were essentially equal. The G value for H{sub 2} production from alpha radiation was somewhat higher. Thus, the model has two equations, one for beta/gamma radiation and one for alpha radiation. Experimental studies have also indicated that both G values are decreased by the presence of nitrate and nitrite ions in the waste. These are the main scavengers for the precursors of H{sub 2} in the waste; thus the equations that were developed predict G values for hydrogen production as a function of the concentrations of these two ions in waste. Knowing the beta/gamma and alpha heat loads in the waste allows one to predict the total generation rate for hydrogen in a tank. With this prediction a ventilation rate can be established for each tank to ensure that a flammable mixture is not formed in the vapor space in a tank. Recently personnel at Hanford have developed a slightly different model for predicting hydrogen G values. Their model includes the same precursor for H{sub 2} as the SRS model but also includes an additional precursor not in the SRS model. Including the second precursor for H{sub 2} leads to different empirical equations for predicting the G values for H{sub 2} as a function of the nitrate and nitrite concentrations in

  14. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond

    2013-01-01

    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  15. Analysis of the dynamics of hydrogen ingress to secondary sodium after the replacement of the steam generator stages of the BN-600 power unit

    International Nuclear Information System (INIS)

    The article presents the calculation methodology of hydrogen ingress rate into secondary circuit sodium of the BN-600 power unit. The sources and the mechanism of the hydrogen ingress after the replacement of a lot of the PGN-200M steam generator stages within the scope of work on the power unit operation lifetime extension were defined. The hydrogen ingress rate after impending replacements of steam generator stages was estimated

  16. Hydrogen generation during melter feed preparation of Tank 42 sludge and salt washed loaded CST in the Defense Waste Processing Facility

    Energy Technology Data Exchange (ETDEWEB)

    Daniel, W.E.

    1999-12-08

    The main objective of these scoping tests was to measure the rate of hydrogen generation in a series of experiments designed to duplicate the expected SRAT and SME processing conditions in laboratory scale vessels. This document details the testing performed to determine the maximum hydrogen generation expected with a coupled flowsheet of sludge, loaded CST [crystalline silicotitanate], and frit.

  17. Evaluation of Hybrid Power Plants using Biomass, Photovoltaics and Steam Electrolysis for Hydrogen and Power Generation

    Science.gov (United States)

    Petrakopoulou, F.; Sanz, J.

    2014-12-01

    Steam electrolysis is a promising process of large-scale centralized hydrogen production, while it is also considered an excellent option for the efficient use of renewable solar and geothermal energy resources. This work studies the operation of an intermediate temperature steam electrolyzer (ITSE) and its incorporation into hybrid power plants that include biomass combustion and photovoltaic panels (PV). The plants generate both electricity and hydrogen. The reference -biomass- power plant and four variations of a hybrid biomass-PV incorporating the reference biomass plant and the ITSE are simulated and evaluated using exergetic analysis. The variations of the hybrid power plants are associated with (1) the air recirculation from the electrolyzer to the biomass power plant, (2) the elimination of the sweep gas of the electrolyzer, (3) the replacement of two electric heaters with gas/gas heat exchangers, and (4) the replacement two heat exchangers of the reference electrolyzer unit with one heat exchanger that uses steam from the biomass power plant. In all cases, 60% of the electricity required in the electrolyzer is covered by the biomass plant and 40% by the photovoltaic panels. When comparing the hybrid plants with the reference biomass power plant that has identical operation and structure as that incorporated in the hybrid plants, we observe an efficiency decrease that varies depending on the scenario. The efficiency decrease stems mainly from the low effectiveness of the photovoltaic panels (14.4%). When comparing the hybrid scenarios, we see that the elimination of the sweep gas decreases the power consumption due to the elimination of the compressor used to cover the pressure losses of the filter, the heat exchangers and the electrolyzer. Nevertheless, if the sweep gas is used to preheat the air entering the boiler of the biomass power plant, the efficiency of the plant increases. When replacing the electric heaters with gas-gas heat exchangers, the

  18. Degradation of 2,4,6-Trichlorophenol Using Hydrogen Peroxide Catalyzed by Nanoscale Zero-Valent Iron Supported on Ion Exchange Resin.

    Science.gov (United States)

    Tai, Chao; She, Jiaping; Yin, Yongguang; Zhao, Tongqian; Wu, Li

    2016-06-01

    Nanoscale zero-valent iron (NZVI) supported on ion exchange resin was prepared and characterized by scanning electron microscope and energy dispersive spectroscopy, with a simple model developed for describing the catalyst. The degradation of 2,4,6-trichlorophenol (2,4,6-TCP) by hydrogen peroxide using NZVI supported on ion exchange resin as the catalyst, was studied. The results showed that 2,4,6-TCP with a concentration of 1 mmol L(-1) could be well degraded into low molecule weight organic acids in two hours. The optimized condition was as follows: pH, 3.0; temperature, 35 degrees C; catalyst dosage, 1.5 g; and hydrogen peroxide, 0.16 mmol L(-1). The catalyst has good reusability, with no catalytic efficiency decreasing even after ten times recycles. A possible mechanism of 2,4,6-TCP degradation was proposed, based on the products indentified by GC-MS after derived using trimethylsulfonium hydroxide. PMID:27427643

  19. Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

    Science.gov (United States)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

    2012-01-01

    We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

  20. Down-conversion photoluminescence sensitizing plasmonic silver nanoparticles on ZnO nanorods to generate hydrogen by water splitting photochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kung, Po-Yen; Huang, Li-Wen; Shen, Tin-Wei; Wang, Wen-Lin; Su, Yen-Hsun [Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan (China); Lin, Melody I. [Department of Physics, University of California, Berkeley, California, 94720 (United States)

    2015-01-12

    Silver nanoparticles fabricated onto the surface of the ZnO nanorods form the photoanode and generate photoelectric current due to surface plasmon resonance, which serves as anode electrodes in photoelectrochemical hydrogen production. In order to increase the absorption spectrum of photoanode, organic pigments were utilized as photo-sensitizers to generate down-conversion photoluminescence to excite surface plasmon resonances of silver nanoparticles. The way of using light to carry the energy in electronic scattering regime runs the system for the enhancement of solar water splitting efficiency. It was significantly tuned in environmentally sustainable applications for power generation and development of alternative energy.

  1. The hydrogen emission of young stellar objects : Key science for next-generation instruments and facilities

    NARCIS (Netherlands)

    Garcia, Paulo J. V.; Benisty, Myriam; Rajabi, Samira; Dougados, Catherine; Massi, Fabrizzio; Bacciotti, Francesca; Le Bouquin, Jean-Baptiste; Malbet, Fabien; Podio, Linda; Renard, Stephanie; Whelan, Emma

    2010-01-01

    The hydrogen emission line is a defining characteristic of young stellar objects probing the planet forming regions of the disks. The limiting sensitivity of current interferometers has precluded it's detailed study. We'll review our current understanding of hydrogen emission, recent results and pro

  2. Engineering design and testing of a ground water remediation system using electrolytically generated hydrogen with a palladium catalyst for dehalogenation of chlorinated hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz, R.

    1997-12-01

    Recent studies have shown that dissolved hydrogen causes rapid dehalogenation of chlorinated hydrocarbons in the presence of a palladium catalyst. The speed and completeness of these reactions offer advantages in designing remediation technologies for certain ground water contamination problems. However, a practical design challenge arises in the need to saturate the aqueous phase with hydrogen in an expeditious manner. To address this issue, a two-stage treatment reactor has been developed. The first stage consists of an electrolytic cell that generates hydrogen by applying a voltage potential across the influent water stream. The second stage consists of a catalyst column of palladium metal supported on alumina beads. A bench-scale reactor has been used to test this design for treating ground water contaminated with trichloroethene and other chlorinated hydrocarbons. In influent streams containing contaminant concentrations up to 4 ppm, initial results confirm that destruction efficiencies greater than 95% may be achieved with residence times short enough to allow practical implementation in specially designed flow-through treatment wells. Results from the bench-scale tests are being used to design a pilot ground water treatment system.

  3. Pt/PIC催化还原芳香硝基化合物制备芳胺%Pt/PIC catalyzed hydrogenation of aromatic nitro compounds to arylamine

    Institute of Scientific and Technical Information of China (English)

    张渊; 张瑞; 黄军; 朱福和

    2012-01-01

    制备了一种多孔离子型高聚物(简称离聚物PIC),利用扫描电镜、透射电镜等一系列手段对离聚物PIC的形貌、结构进行表征,并制备负载型纳米铂催化剂(Pt/PIC)用于温和条件下芳胺(如对苯二胺、邻苯二胺、2-溴苯胺等)的合成实验中。实验表明:在1 atm H2条件下,该Pt/PIC催化剂对于芳香硝基化合物还原氢化反应具有高的催化活性和选择性,尤其是还原性基团如醛基、酮基、氰基,在氢化还原相应硝基芳基化合物过程中未受影响,且高产率得到相应芳胺。%A porous ionic copolymer(PIC) was prepared and characterized by SEM,BET,and TEM.The morphology and structure was investigated.And a supported Pt nano-catalyst(Pt/PIC) was prepared and used for the synthesis of anilines(such as p-phenylenediamine,o-diaminobenzene,2-Bromoaniline,et al.) under mild conditions.The study results showed that Pt/PIC catalyst was highly active and selective for the hydrogenation of nitro aromatic compounds under 1 atm H2.Reducible groups such as aldehyde,ketone and nitrile were not attacked during the hydrogenation of the corresponding nitro compounds,and the corresponding anilines were obtained with high yield.

  4. Novel material for second harmonic generation: 3-Amino-1,2,4-triazolinium(1+) hydrogen L-tartrate

    Science.gov (United States)

    Matulková, Irena; Němec, Ivan; Císařová, Ivana; Němec, Petr; Mička, Zdeněk

    2007-05-01

    The X-ray structural analysis of 3-amino-1,2,4-triazolinium(1+) hydrogen L-tartrate has been carried out. This organic salt crystallises in the monoclinic space group P2 1, a = 7.7130(2) Å, b = 6.7690(2) Å, c = 9.2170(3) Å, β = 95.726(2)°, V = 478.81(2) Å 3, Z = 2, R = 0.0255 for 5922 observed reflections. The crystal structure is formed by a 3D network of hydrogen L-tartrate anions (interconnected by O-H ⋯O hydrogen bonds) with 3-amino-1,2,4-triazolinium(1+) cations located in the cavities of this network and connected with anions via N-H ⋯O and O-H ⋯N hydrogen bonds. The FTIR and FT Raman spectra were recorded, calculated and discussed. Quantitative measurements of second harmonic generation of powdered 3-amino-1,2,4-triazol-4-ium hydrogen L-tartrate at 800 nm were performed and a relative efficiency of 50% (compared to KDP) was observed.

  5. Model biogas steam reforming in a thin Pd-supported membrane reactor to generate clean hydrogen for fuel cells

    Science.gov (United States)

    Iulianelli, A.; Liguori, S.; Huang, Y.; Basile, A.

    2015-01-01

    Steam reforming of a model biogas mixture is studied for generating clean hydrogen by using an inorganic membrane reactor, in which a composite Pd/Al2O3 membrane separates part of the produced hydrogen through its selective permeation. The characteristics of H2 perm-selectivity of the fresh membrane is expressed in terms of H2/N2 ideal selectivity, in this case equal to 4300. Concerning biogas steam reforming reaction, at 380 °C, 2.0 bar H2O:CH4 = 3:1, GHSV = 9000 h-1 the permeate purity of the recovered hydrogen is around 96%, although the conversion (15%) and hydrogen recovery (>20%) are relatively low; on the contrary, at 450 °C, 3.5 bar H2O:CH4 = 4:1, GHSV = 11000 h-1 the conversion is increased up to more than 30% and the recovery of hydrogen to about 70%. This novel work constitutes a reference study for new developments on biogas steam reforming reaction in membrane reactors.

  6. Optimization of efficiency and energy density of passive micro fuel cells and galvanic hydrogen generators

    CERN Document Server

    Hahn, Robert; Krumbholz, Steffen; Reichl, Herbert

    2008-01-01

    A PEM micro fuel cell system is described which is based on self-breathing PEM micro fuel cells in the power range between 1 mW and 1W. Hydrogen is supplied with on-demand hydrogen production with help of a galvanic cell, that produces hydrogen when Zn reacts with water. The system can be used as a battery replacement for low power applications and has the potential to improve the run time of autonomous systems. The efficiency has been investigated as function of fuel cell construction and tested for several load profiles.

  7. All-Vanadium Dual Circuit Redox Flow Battery for Renewable Hydrogen Generation and Desulfurisation

    OpenAIRE

    Peljo, Pekka Eero; Vrubel, Heron; Amstutz, Veronique; Pandard, Justine; Morgado, Joana; Santasalo-Aarnio, Annukka; Lloyd, David; Gumy, Frederic; Dennison, C R; Toghill, Kathryn; Girault, Hubert

    2016-01-01

    An all-vanadium dual circuit redox flow battery is an electrochemical energy storage system capable to function as a conventional battery, but also to produce hydrogen and perform desulfurization when surplus of electricity is available by chemical discharge of the battery electrolytes. The hydrogen reactor chemically discharging the negative electrolyte has been designed and scaled up to kW scale, while different options to discharge the positive electrolyte have been evaluated, including ox...

  8. Helium-Hydrogen generation arising from the 55Fe(n,x) reaction and its impact on fusion reactor

    International Nuclear Information System (INIS)

    In order to design the fusion reactor components neutron induced reaction (n,p) and (n,α) on the generated 55Fe to be studied. Detail study of 55Fe(n,p) reaction cross-section has been performed earlier. The present study describes the hydrogen and helium production from 55Fe(n,p) and 55Fe(n,α) reactions and its impact on fusion reactor

  9. High Efficiency Generation of Hydrogen Fuels Using Nuclear Power - for the period August 1, 1999 through October 31, 1999

    Energy Technology Data Exchange (ETDEWEB)

    L. C. Brown

    2000-01-01

    OAK B188 High Efficiency Generation of Hydrogen Fuels Using Nuclear Power - for the period August 1, 1999 through October 31, 1999. The highlights for this period are: (1) The methodologies for searching the literature for potentially attractive thermochemical water-splitting cycles, storing cycle and reference data, and screening the cycles have been established; and (2) The water-splitting cycle screening criteria were established on schedule.

  10. Steam reforming of ethanol over Ni/support catalysts for generation of hydrogen for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Denis, Andrzej; Grzegorczyk, Wieslaw; Gac, Wojciech; Machocki, Andrzej [University of Maria Curie-Sklodowska, Faculty of Chemistry, Department of Chemical Technology, 3 Maria Curie-Sklodowska Square, 20-031 Lublin (Poland)

    2008-09-30

    The paper reports experimental results concerning the influence of the support nature (TiO{sub 2}, ZnO, Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-Fe{sub 2}O{sub 3}) of nickel catalysts on their activity, selectivity and coking phenomenon in the steam reforming of ethanol in the range of 570-870K. The chemical transformations of ethanol occurring on the catalyst support make its chemical nature an important factor affecting the productivity and selectivity of the process. It was found that the most suitable supports in nickel catalysts designed for hydrogen generation in the steam reforming of ethanol are ZnO and TiO{sub 2}. Taking into consideration both the efficiency of hydrogen generation and the intensity of carbon deposition, the optimum temperature of the process of the steam reforming of ethanol is below 750K. An improvement in the selectivity of hydrogen generation and diminishing of the formation of undesirable products may be obtained by promoting nickel catalysts with sodium. (author)

  11. Modification of TiO2 nanotubes arrays by CdS and their photoelectrocatalytic hydrogen generation properties

    Institute of Scientific and Technical Information of China (English)

    ZHANG JianLing; ZHANG XingWang; LEI LeCheng

    2008-01-01

    In order to realize hydrogen generation under visible light, novel CdS/TiO2 nanotubes arrays are de-veloped by electrochemical anodization of Ti in 0.15 mol/L NH4F+ 0.08 mol/l. H2C2O4 electrolyte. The diameter of the nanotube is 80-100 nm and the length is approximately 550 nm. The CdS nano-particles are deposited on the TiO2 nanotubes arrays by chemical bath deposition (CBD) in the ammonia-thiourea system. A 300 W Xe lamp is used as the light source, CdS/TiO2 nanotube arrays are used as the photoanode with the application of 1.0 V bath voltage, and 0.1 mol/L Na2S + 0.04 mol/L Na2SO3 solution is used as the electrolyte, then the rate of photoelectrocatalytic hydrogen generation is 245.4 μl/(h·cm2). This opens new perspectives for photoelectrocatalytic hydrogen generation by using CdS/TiO2 nanotubes arrays.

  12. PVP-stabilized Ru–Rh nanoparticles as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

    International Nuclear Information System (INIS)

    Herein, the utilization of poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles (3.4 ± 1.4 nm) as highly efficient catalysts in the hydrolysis of ammonia borane for hydrogen generation is reported. They are prepared by co-reduction of ruthenium and rhodium metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy-energy dispersive X-ray spectroscopy, ultraviolet–visible spectroscopy, and X-ray photoelectron spectroscopy. They are durable and highly efficient catalysts for hydrogen generation from the hydrolysis of ammonia borane even at very low concentrations and temperature, providing average turnover frequency of 386 mol H2 (mol cat)−1 min−1 and maximum hydrogen generation rate of 10,680 L H2 min−1 (mol cat)−1. Poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles also provide activation energy of 47.4 ± 2.1 kJ/mol for the hydrolysis of ammonia borane. - Highlights: • Ru-Rh@PVP NPs provide a TOF of 386 mol H2 (mol cat)−1 min−1 for hydrolysis of AB. • Maximum HG rate is 9680 L H2 min−1 (mol cat)−1 for the hydrolysis of AB. • Activation energy is 47.4 ± 2.1 kJ mol−1 for the hydrolysis of AB

  13. The Development of Fuel Cell Technology for Electric Power Generation - From Spacecraft Applications to the Hydrogen Economy

    Science.gov (United States)

    Scott, John H.

    2005-01-01

    The fuel cell uses a catalyzed reaction between a fuel and an oxidizer to directly produce electricity. Its high theoretical efficiency and low temperature operation made it a subject of much study upon its invention ca. 1900, but its relatively high life cycle costs kept it as "solution in search of a problem" for its first half century. The first problem for which fuel cells presented a cost effective solution was, starting in the 1960's that of a power source for NASA's manned spacecraft. NASA thus invested, and continues to invest, in the development of fuel cell power plants for this application. However, starting in the mid-1990's, prospective environmental regulations have driven increased governmental and industrial interest in "green power" and the "Hydrogen Economy." This has in turn stimulated greatly increased investment in fuel cell development for a variety of terrestrial applications. This investment is bringing about notable advances in fuel cell technology, but these advances are often in directions quite different from those needed for NASA spacecraft applications. This environment thus presents both opportunities and challenges for NASA's manned space program.

  14. Generation of a VUV-to-visible Raman frequency comb in hydrogen-filled kagom\\'e photonic crystal fiber

    CERN Document Server

    Mridha, M K; Bauerschmidt, S T; Abdolvand, A; Russell, P St J

    2016-01-01

    We report the generation of a purely vibrational Raman comb, extending from the vacuum ultraviolet (184 nm) to the visible (478 nm), in hydrogen-filled kagom\\'e-style photonic crystal fiber pumped at 266 nm. Stimulated Raman scattering and molecular modulation processes are enhanced by higher Raman gain in the ultraviolet. Owing to the pressure-tunable normal dispersion landscape of the fiber-gas system in the ultraviolet, higher-order anti-Stokes bands are generated preferentially in higher-order fiber modes. The results pave the way towards tunable fiber-based sources of deep- and vacuum ultraviolet light for applications in, e.g., spectroscopy and biomedicine.

  15. A third-generation dispersion and third-generation hydrogen bonding corrected PM6 method: PM6-D3H+

    Directory of Open Access Journals (Sweden)

    Jimmy C. Kromann

    2014-06-01

    Full Text Available We present new dispersion and hydrogen bond corrections to the PM6 method, PM6-D3H+, and its implementation in the GAMESS program. The method combines the DFT-D3 dispersion correction by Grimme et al. with a modified version of the H+ hydrogen bond correction by Korth. Overall, the interaction energy of PM6-D3H+ is very similar to PM6-DH2 and PM6-DH+, with RMSD and MAD values within 0.02 kcal/mol of one another. The main difference is that the geometry optimizations of 88 complexes result in 82, 6, 0, and 0 geometries with 0, 1, 2, and 3 or more imaginary frequencies using PM6-D3H+ implemented in GAMESS, while the corresponding numbers for PM6-DH+ implemented in MOPAC are 54, 17, 15, and 2. The PM6-D3H+ method as implemented in GAMESS offers an attractive alternative to PM6-DH+ in MOPAC in cases where the LBFGS optimizer must be used and a vibrational analysis is needed, e.g., when computing vibrational free energies. While the GAMESS implementation is up to 10 times slower for geometry optimizations of proteins in bulk solvent, compared to MOPAC, it is sufficiently fast to make geometry optimizations of small proteins practically feasible.

  16. The crystal structure, vibrational spectra, thermal behaviour and second harmonic generation of aminoguanidinium(1+) hydrogen L-tartrate monohydrate

    Science.gov (United States)

    Macháčková, Zorka; Němec, Ivan; Teubner, Karel; Němec, Petr; Vaněk, Přemysl; Mička, Zdeněk

    2007-04-01

    Aminoguanidinium(1+) hydrogen L-tartrate monohydrate was prepared by crystallisation from aqueous solution and X-ray structural analysis was carried out. The substance crystallises in the orthorhombic system in space group P2 12 12 1, a = 7.1380(2) Å, b = 9.9700(4) Å, c = 14.0790(6) Å, V = 1001.94(7) Å 3, Z = 4, R = 0.0271 for 2272 observed reflections. The crystal structure consists of a 3D framework formed by hydrogen tartrate anions and water molecules with incorporated aminoguanidinium(1+) cations connected by a system of hydrogen bonds. The FTIR and FT Raman spectra of natural and N,O-deuterated compounds were measured and discussed at laboratory temperature. DSC measurements were carried out in the temperature range from 95 to 380 K. A weak anomaly was observed at a temperature of 268 K. Quantitative measurements of second harmonic generation of powdered aminoguanidinium(1+) hydrogen tartrate monohydrate at 800 nm were performed relative to KDP and a relative efficiency of 14% was observed.

  17. Nano-design of quantum dot-based photocatalysts for hydrogen generation using advanced surface molecular chemistry

    KAUST Repository

    Yu, Weili

    2015-01-01

    Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.

  18. Methane Formation by Flame-Generated Hydrogen Atoms in the Flame Ionization Detector

    DEFF Research Database (Denmark)

    Holm, Torkil; Madsen, Jørgen Øgaard

    1996-01-01

    The precombustion degradation of organic compounds in the flame ionization detector has been studied (1) by heating the additives in hydrogen in a quartz capillary and analyzing the reaction products by GC and (2) by following the degradation of the additives in a hydrogen flame, by means of a thin...... fused silica probe inserted from the bottom of the flame and connected to the ion source of a mass spectrometer. The results show that the thermic hydrogenolysis of hydrocarbons at flame temperatures produces mixtures of methane, ethene, and ethyne. In the flame, however, ethyne, benzene, isobutane...... atoms, which are formed in the burning hydrogen and which diffuse into the inner core of the flame. The quantitative formation of methane appears to explain the "equal per carbon" rule for the detector response of hydrocarbons, since all carbons are "exchanged" for methane molecules....

  19. Advanced chemical hydride-based hydrogen generation/storage system for fuel cell vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Breault, R.W.; Rolfe, J. [Thermo Power Corp., Waltham, MA (United States)

    1998-08-01

    Because of the inherent advantages of high efficiency, environmental acceptability, and high modularity, fuel cells are potentially attractive power supplies. Worldwide concerns over clean environments have revitalized research efforts on developing fuel cell vehicles (FCV). As a result of intensive research efforts, most of the subsystem technology for FCV`s are currently well established. These include: high power density PEM fuel cells, control systems, thermal management technology, and secondary power sources for hybrid operation. For mobile applications, however, supply of hydrogen or fuel for fuel cell operation poses a significant logistic problem. To supply high purity hydrogen for FCV operation, Thermo Power`s Advanced Technology Group is developing an advanced hydrogen storage technology. In this approach, a metal hydride/organic slurry is used as the hydrogen carrier and storage media. At the point of use, high purity hydrogen will be produced by reacting the metal hydride/organic slurry with water. In addition, Thermo Power has conceived the paths for recovery and regeneration of the spent hydride (practically metal hydroxide). The fluid-like nature of the spent hydride/organic slurry will provide a unique opportunity for pumping, transporting, and storing these materials. The final product of the program will be a user-friendly and relatively high energy storage density hydrogen supply system for fuel cell operation. In addition, the spent hydride can relatively easily be collected at the pumping station and regenerated utilizing renewable sources, such as biomass, natural, or coal, at the central processing plants. Therefore, the entire process will be economically favorable and environmentally friendly.

  20. Preliminary analysis of an hydrogen generator system based on nuclear energy in the Laguna Verde site

    International Nuclear Information System (INIS)

    The shortage of fossil fuels in the next future, as well as the growing one demand of energetics and the high cost of the production of alternating fuels, it forces us to take advantage of to the maximum the fossil fuel with the one which we count and to look for the form of producing alternating fuels at a low cost and better even if these supply sources are reliable and non pollutants. It is intended a solution to the shortage of fuel; to use the thermal energy liberated of some appropriate nuclear reactor to be able to obtain a fuel but clean and relatively cheap as it is the hydrogen. In the first place the methods were looked for to produce hydrogen using thermal energy, later it was analyzed the temperature liberated by the existent nuclear reactors as well as the advanced designs, according to this liberated temperature settled down that the methods but feasible to produce hydrogen its were the one of reformed with water stream of the natural gas (methane) and the other one of the S-I thermochemical cycle, and the nuclear reactors that give the thermal energy for this production they are those of gas of high temperature. Once established the processes and the appropriate reactors, it was analyzed the site of Laguna Verde, with relationship to the free space to be able to place the reactor and the plant producer of hydrogen, as well as the direction in which blow the dominant winds and the near towns to the place, it was carried out an analysis of some explosion of tanks that could store hydrogen and the damage that its could to cause depending from the distance to which its were of the fire. Finally it was carried out an evaluation of capital and of operation costs for those two methods of hydrogen production. (Author)

  1. Integration of first and second generation biofuels: Fermentative hydrogen production from wheat grain and straw

    NARCIS (Netherlands)

    Panagiotopoulos, I.A.; Bakker, R.R.C.; Vrije, de G.J.; Claassen, P.A.M.; Koukios, E.G.

    2013-01-01

    Integrating of lignocellulose-based and starch-rich biomass-based hydrogen production was investigated by mixing wheat straw hydrolysate with a wheat grain hydrolysate for improved fermentation. Enzymatic pretreatment and hydrolysis of wheat grains led to a hydrolysate with a sugar concentration of

  2. Pentlandite rocks as sustainable and stable efficient electrocatalysts for hydrogen generation

    Science.gov (United States)

    Konkena, Bharathi; junge Puring, Kai; Sinev, Ilya; Piontek, Stefan; Khavryuchenko, Oleksiy; Dürholt, Johannes P.; Schmid, Rochus; Tüysüz, Harun; Muhler, Martin; Schuhmann, Wolfgang; Apfel, Ulf-Peter

    2016-01-01

    The need for sustainable catalysts for an efficient hydrogen evolution reaction is of significant interest for modern society. Inspired by comparable structural properties of [FeNi]-hydrogenase, here we present the natural ore pentlandite (Fe4.5Ni4.5S8) as a direct ‘rock' electrode material for hydrogen evolution under acidic conditions with an overpotential of 280 mV at 10 mA cm−2. Furthermore, it reaches a value as low as 190 mV after 96 h of electrolysis due to surface sulfur depletion, which may change the electronic structure of the catalytically active nickel–iron centres. The ‘rock' material shows an unexpected catalytic activity with comparable overpotential and Tafel slope to some well-developed metallic or nanostructured catalysts. Notably, the ‘rock' material offers high current densities (≤650 mA cm−2) without any loss in activity for approximately 170 h. The superior hydrogen evolution performance of pentlandites as ‘rock' electrode labels this ore as a promising electrocatalyst for future hydrogen-based economy. PMID:27461840

  3. Pentlandite rocks as sustainable and stable efficient electrocatalysts for hydrogen generation

    Science.gov (United States)

    Konkena, Bharathi; Junge Puring, Kai; Sinev, Ilya; Piontek, Stefan; Khavryuchenko, Oleksiy; Dürholt, Johannes P.; Schmid, Rochus; Tüysüz, Harun; Muhler, Martin; Schuhmann, Wolfgang; Apfel, Ulf-Peter

    2016-07-01

    The need for sustainable catalysts for an efficient hydrogen evolution reaction is of significant interest for modern society. Inspired by comparable structural properties of [FeNi]-hydrogenase, here we present the natural ore pentlandite (Fe4.5Ni4.5S8) as a direct `rock' electrode material for hydrogen evolution under acidic conditions with an overpotential of 280 mV at 10 mA cm-2. Furthermore, it reaches a value as low as 190 mV after 96 h of electrolysis due to surface sulfur depletion, which may change the electronic structure of the catalytically active nickel-iron centres. The `rock' material shows an unexpected catalytic activity with comparable overpotential and Tafel slope to some well-developed metallic or nanostructured catalysts. Notably, the `rock' material offers high current densities (<=650 mA cm-2) without any loss in activity for approximately 170 h. The superior hydrogen evolution performance of pentlandites as `rock' electrode labels this ore as a promising electrocatalyst for future hydrogen-based economy.

  4. Environmental meticillin-resistant Staphylococcus aureus (MRSA) disinfection using dry-mist-generated hydrogen peroxide

    DEFF Research Database (Denmark)

    Bartels, M.D.; Kristoffersen, K.; Slotsbjerg, T.;

    2008-01-01

    Meticillin-resistant Staphylococcus aureus (MRSA) is a major problem in hospitals worldwide. Hand hygiene is recognised as crucial in limiting the spread of MRSA but less is known about the role of MRSA reservoirs in the inanimate hospital environment. We evaluated the effect of hydrogen peroxide...

  5. Water leak detection in sodium heated steam generators through measurement of hydrogen concentration in sodium

    International Nuclear Information System (INIS)

    This report includes a description of apparatus for measuring hydrogen concentration in the secondary sodium system of the PHENIX reactor. The calibration method and results obtained since the commissioning of the reactor are also described. Mention is made of improvements to be built into SUPER PHENIX

  6. Pentlandite rocks as sustainable and stable efficient electrocatalysts for hydrogen generation.

    Science.gov (United States)

    Konkena, Bharathi; Junge Puring, Kai; Sinev, Ilya; Piontek, Stefan; Khavryuchenko, Oleksiy; Dürholt, Johannes P; Schmid, Rochus; Tüysüz, Harun; Muhler, Martin; Schuhmann, Wolfgang; Apfel, Ulf-Peter

    2016-01-01

    The need for sustainable catalysts for an efficient hydrogen evolution reaction is of significant interest for modern society. Inspired by comparable structural properties of [FeNi]-hydrogenase, here we present the natural ore pentlandite (Fe4.5Ni4.5S8) as a direct 'rock' electrode material for hydrogen evolution under acidic conditions with an overpotential of 280 mV at 10 mA cm(-2). Furthermore, it reaches a value as low as 190 mV after 96 h of electrolysis due to surface sulfur depletion, which may change the electronic structure of the catalytically active nickel-iron centres. The 'rock' material shows an unexpected catalytic activity with comparable overpotential and Tafel slope to some well-developed metallic or nanostructured catalysts. Notably, the 'rock' material offers high current densities (≤650 mA cm(-2)) without any loss in activity for approximately 170 h. The superior hydrogen evolution performance of pentlandites as 'rock' electrode labels this ore as a promising electrocatalyst for future hydrogen-based economy. PMID:27461840

  7. Design of a Fuel Processor System for Generating Hydrogen for Automotive Applications

    Science.gov (United States)

    Kolavennu, Panini K.; Telotte, John C.; Palanki, Srinivas

    2006-01-01

    The objective of this paper is to design a train of tubular reactors that use a methane feed to produce hydrogen of the desired purity so that it can be utilized by a fuel cell for automotive applications. Reaction engineering principles, which are typically covered at the undergraduate level, are utilized to design this reactor train. It is shown…

  8. A two-stage bio hydrogen process for energy generation from municipal solid wastes

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo-Benitez, J. a.; Poggi-Varaldo, H. M.

    2009-07-01

    Energy supply and disposal of solid wastes are two big challenges that great cities face at the present time. Several experts have shown that hydrogen is the fuel of the future, due to their high energy content (three times more than that of the gasoline) and its clean combustion. (Author)

  9. Hydrogen peroxide generation in caco-2 cell culture medium by addition of phenolic compounds: effect of ascorbic acid.

    Science.gov (United States)

    Roques, Sylvie Cambon; Landrault, Nicolas; Teissèdre, Pierre-Louis; Laurent, Caroline; Besançon, Pierre; Rouane, Jean-Max; Caporiccio, Bertrand

    2002-05-01

    Phenolic compounds have recently attracted special attention due to their beneficial health effects; their intestinal absorption and bioavailability need, therefore, to be investigated and Caco-2 cell culture model appeared as a promising tool. We have shown herein that the addition of a grape seed extract (GSE) to Dulbecco's modified Eagle's medium (DMEM) used for Caco-2 cell culture leads to a substantial loss of catechin, epicatechin and B2 and B3 dimers from GSE in the medium after 24 h and to a production of hydrogen peroxide (H2O2). When 1420 microM ascorbic acid is added to the DMEM, such H2O2 production was prevented. This hydrogen peroxide generation substantially involves inorganic salts from the DMEM. We recommend that ascorbic acid be added to circumvent such a risk. PMID:12150547

  10. FINAL TECHNICAL REPORT for grant DE-FG02-93ER14353 "Carbon-Hydrogen Bond Functionalization Catalyzed by Transition Metal Systems"

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Alan S

    2012-05-21

    Alkanes are our most abundant organic resource but are highly resistant to selective chemical transformations. Alkenes (olefins) by contrast are the single most versatile class of molecules for selective transformations, and are intermediates in virtually every petrochemical process as well as a vast range of commodity and fine chemical processes. Over the course of this project we have developed the most efficient catalysts to date for the selective conversion of alkanes to give olefins, and have applied these catalysts to other dehydrogenation reactions. We have also developed some of the first efficient catalysts for carbonylation of alkanes and arenes to give aldehydes. The development of these catalysts has been accompanied by elucidation of the mechanism of their operation and the factors controlling the kinetics and thermodynamics of C-H bond activation and other individual steps of the catalytic cycles. This fundamental understanding will allow the further improvement of these catalysts, as well as the development of the next generation of catalysts for the functionalization of alkanes and other molecules containing C-H bonds.

  11. Drinking hydrogen water and intermittent hydrogen gas exposure, but not lactulose or continuous hydrogen gas exposure, prevent 6-hydorxydopamine-induced Parkinson’s disease in rats

    Directory of Open Access Journals (Sweden)

    Ito Mikako

    2012-05-01

    Full Text Available Abstract Background Lactulose is a synthetic disaccharide that can be catalyzed only by intestinal bacteria in humans and rodents, and a large amount of hydrogen is produced by bacterial catalysis of lactulose. We previously reported marked effects of ad libitum administration of hydrogen water on prevention of a rat model of Parkinson’s disease (PD. Methods End-alveolar breath hydrogen concentrations were measured in 28 healthy subjects and 37 PD patients, as well as in 9 rats after taking hydrogen water or lactulose. Six-hydroxydopamine (6-OHDA-induced hemi-PD model was stereotactically generated in rats. We compared effects of hydrogen water and lactulose on prevention of PD. We also analyzed effects of continuous and intermittent administration of 2% hydrogen gas. Results Hydrogen water increased breath hydrogen concentrations from 8.6 ± 2.1 to 32.6 ± 3.3 ppm (mean and SEM, n = 8 in 10 min in healthy subjects. Lactulose increased breath hydrogen concentrations in 86% of healthy subjects and 59% of PD patients. Compared to monophasic hydrogen increases in 71% of healthy subjects, 32% and 41% of PD patients showed biphasic and no increases, respectively. Lactulose also increased breath hydrogen levels monophasically in 9 rats. Lactulose, however, marginally ameliorated 6-OHDA-induced PD in rats. Continuous administration of 2% hydrogen gas similarly had marginal effects. On the other hand, intermittent administration of 2% hydrogen gas prevented PD in 4 of 6 rats. Conclusions Lack of dose responses of hydrogen and the presence of favorable effects with hydrogen water and intermittent hydrogen gas suggest that signal modulating activities of hydrogen are likely to be instrumental in exerting a protective effect against PD.

  12. Toward enhanced hydrogen generation from water using oxygen permeating LCF membranes

    KAUST Repository

    Wu, Xiao-Yu

    2015-01-01

    © the Owner Societies. Hydrogen production from water thermolysis can be enhanced by the use of perovskite-type mixed ionic and electronic conducting (MIEC) membranes, through which oxygen permeation is driven by a chemical potential gradient. In this work, water thermolysis experiments were performed using 0.9 mm thick La0.9Ca0.1FeO3-δ (LCF-91) perovskite membranes at 990 °C in a lab-scale button-cell reactor. We examined the effects of the operating conditions such as the gas species concentrations and flow rates on the feed and sweep sides on the water thermolysis rate and oxygen flux. A single step reaction mechanism is proposed for surface reactions, and three-resistance permeation models are derived. Results show that water thermolysis is facilitated by the LCF-91 membrane especially when a fuel is added to the sweep gas. Increasing the gas flow rate and water concentration on the feed side or the hydrogen concentration on the sweep side enhances the hydrogen production rate. In this work, hydrogen is used as the fuel by construction, so that a single-step surface reaction mechanism can be developed and water thermolysis rate parameters can be derived. Both surface reaction rate parameters for oxygen incorporation/dissociation and hydrogen-oxygen reactions are fitted at 990 °C. We compare the oxygen fluxes in water thermolysis and air separation experiments, and identify different limiting steps in the processes involving various oxygen sources and sweep gases for this 0.9 mm thick LCF-91 membrane. In the air feed-inert sweep case, the bulk diffusion and sweep side surface reaction are the two limiting steps. In the water feed-inert sweep case, surface reaction on the feed side dominates the oxygen permeation process. Yet in the water feed-fuel sweep case, surface reactions on both the feed and sweep sides are rate determining when hydrogen concentration in the sweep side is in the range of 1-5 vol%. Furthermore, long term studies show that the surface

  13. Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions.

    Science.gov (United States)

    Thoi, V Sara; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J

    2013-03-21

    Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products. PMID:23034627

  14. Raising efficiency of hydrogen generation from alkaline water electrolysis - Energy saving

    Energy Technology Data Exchange (ETDEWEB)

    Nikolic, Vladimir M.; Tasic, Gvozden S.; Maksic, Aleksandar D.; Saponjic, Djordje P.; Marceta Kaninski, Milica P. [Vinca Institute of Nuclear Sciences, Department of Physical Chemistry, 11001 Belgrade, POB 522 (RS); Miulovic, Snezana M. [University of Belgrade, Faculty of Physical Chemistry, 11001 Belgrade, POB 276 (RS)

    2010-11-15

    This paper presents an attempt to make the alkaline electrolytic production of hydrogen more efficient by adding in situ activating compounds in ionic and complex form. Cobalt and tungsten based ionic activators (i.a.), added directly into the electrolyte during the electrolytic process, reduce energy requirements per mass unit of hydrogen produced for about 15%, compared to non-activated system, for a number of current densities in a wide temperature range. Energy saving is higher at higher temperatures and on higher current densities. Structural and morphological characteristic of deposit formed on the cathode during the electrolytic process reveal very interesting and unique pattern with highly developed surface area and uniform distribution of the pores. Obtained deposit also exhibit a long term stability. (author)

  15. Photocatalytic hydrogen generation with Ag-loaded LiNbO3

    Indian Academy of Sciences (India)

    Beata Zielińska

    2014-06-01

    In this contribiution LiNbO3 and Ag-loaded LiNbO3 photocatalysts were tested in the reaction of hydrogen evolution. The silver modified samples contained different loading of co-catalyst in the range of 0.5–4 wt%. It was essential to optimize the sample composition to achieve an efficient hydrogen evolution. The optimal sample contained 2 wt% of silver. The detailed analysis indicated that silver was deposited on the surface of LiNbO3 in the form of Ag2O. Therefore, it is supposed that Ag2O was responsible for the enhanced photocatalytic activity in the studied reaction. The crystallographic phases and optical and vibronic properties were examined by X-ray diffraction (XRD) and diffuse reflectance (DR) UV–Vis and resonance Raman spectroscopic methods, respectively. Morphology of the produced samples were studied using a highresolution transmission electron microscope (HRTEM).

  16. Electrodeposited synthesis of self-supported Ni-P cathode for efficient electrocatalytic hydrogen generation

    Directory of Open Access Journals (Sweden)

    Ruixian Wu

    2016-06-01

    Full Text Available One of the key challenges for electrochemical water splitting is the development of low-cost and efficient hydrogen evolution cathode. In this work, a self-supported Ni-P cathode was synthesized by a facile electrodeposition method. The composition and morphology were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The Ni-P cathode performed low onset over-potential, good catalytic activity and long-term stability under neutral and alkaline conditions. The mechanism of Ni-P electrode for hydrogen production was discussed by electrochemical impedance spectroscopy. The excellent performance of Ni-P cathode was mainly attributed to the synergistic effect of phosphate anions and the self-supported feature.

  17. Electrodeposited synthesis of self-supported Ni-P cathode for efficient electrocatalytic hydrogen generation

    Institute of Scientific and Technical Information of China (English)

    Ruixian Wu; Yuming Dong n; Pingping Jiang; Guangli Wang; Yanmei Chen; Xiuming Wu

    2016-01-01

    One of the key challenges for electrochemical water splitting is the development of low-cost and efficient hydrogen evolution cathode. In this work, a self-supported Ni-P cathode was synthesized by a facile electrodeposition method. The composition and morphology were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The Ni-P cathode performed low onset over-potential, good catalytic activity and long-term stability under neutral and alkaline conditions. The mechanism of Ni-P electrode for hydrogen production was discussed by electrochemical impedance spectroscopy. The excellent performance of Ni-P cathode was mainly attributed to the synergistic effect of phosphate anions and the self-supported feature.

  18. Preparation and Characterization of Titanium Dioxide Photoelectrodes for Generation of Hydrogen by Photoelectrochemical Water Splitting

    Directory of Open Access Journals (Sweden)

    Alvaro Realpe

    2015-04-01

    Full Text Available The photoelectrochemical water splitting for the production of hydrogen was evaluated through the preparation of photoelectrodes of different substrates (glass, aluminium, graphite with TiO2 film. The film on each substrate was characterized by scanning electron microscope (SEM and x-ray diffraction (XRD. The results show that the TiO2 was deposited in dispersed form and in small clusters on the surface of the substrate and it had no effect on the crystal structure of the semiconductor; furthermore, good adhesion of the films on substrates was obtained except with graphite substrate. The hydrogen production process was carried out using UV light, halogen light and sunlight as photon sources, and it was evaluated by the current flow through the external circuit of the cell. The highest photocurrent values were obtained with the aluminium photoelectrode, averaging 1092.03 uA.

  19. A polymer electrolyte fuel cell stack for stationary power generation from hydrogen fuel

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, M.S.; Moeller-Holst, S.; Webb, D.M.; Zawodzinski, C.; Gottesfeld, S. [Los Alamos National Lab., NM (United States). Materials Science and Technology Div.

    1998-08-01

    The objective is to develop and demonstrate a 4 kW, hydrogen-fueled polymer electrolyte fuel cell (PEFC) stack, based on non-machined stainless steel hardware and on membrane/electrode assemblies (MEAs) of low catalyst loadings. The stack is designed to operate at ambient pressure on the air-side and can accommodate operation at higher fuel pressures, if so required. This is to be accomplished by working jointly with a fuel cell stack manufacturer, based on a CRADA. The performance goals are 57% energy conversion efficiency hydrogen-to-electricity (DC) at a power density of 0.9 kW/liter for a stack operating at ambient inlet pressures. The cost goal is $600/kW, based on present materials costs.

  20. Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions.

    Science.gov (United States)

    Thoi, V Sara; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J

    2013-03-21

    Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products.

  1. Performance analysis of an integrated biomass gasification and PEMFC (proton exchange membrane fuel cell) system: Hydrogen and power generation

    International Nuclear Information System (INIS)

    The PEMFC (proton exchange membrane fuel cell) is expected to play a significant role in next-generation energy systems. Because most hydrogen that is used as a fuel for PEMFCs is derived from the reforming of natural gas, the use of renewable energy sources such as biomass to produce this hydrogen offers a promising alternative. This study is focused on the performance analysis of an integrated biomass gasification and PEMFC system. The combined heat and power generation output of this integrated system is designed for residential applications, taking into account thermal and electrical demands. A flowsheet model of the integrated PEMFC system is developed and employed to analyze its performance with respect to various key operating parameters. A purification process consisting of a water–gas shift reactor and a preferential oxidation reactor is also necessary in order to reduce the concentration of CO in the synthesis gas to below 10 ppm for subsequent use in the PEMFC. The effect of load level on the performance of the PEMFC system is investigated. Based on an electrical load of 5 kW, it is found that the electrical efficiency of the PEMFC integrated system is 22%, and, when waste heat recovery is considered, the total efficiency of the PEMFC system is 51%. - Highlights: • Performance of a biomass gasification and PEMFC integrated system is analyzed. • A flowsheet model of the PEMFC integrated system is developed. • Effect of biomass sources and key parameters on hydrogen and power generation is presented. • The PEMFC integrated system is designed for small-scale power demand. • Effect of load changes on the performance of PEMFC is investigated

  2. PVP-stabilized Ru–Rh nanoparticles as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Rakap, Murat, E-mail: mrtrakap@gmail.com

    2015-11-15

    Herein, the utilization of poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles (3.4 ± 1.4 nm) as highly efficient catalysts in the hydrolysis of ammonia borane for hydrogen generation is reported. They are prepared by co-reduction of ruthenium and rhodium metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy-energy dispersive X-ray spectroscopy, ultraviolet–visible spectroscopy, and X-ray photoelectron spectroscopy. They are durable and highly efficient catalysts for hydrogen generation from the hydrolysis of ammonia borane even at very low concentrations and temperature, providing average turnover frequency of 386 mol H{sub 2} (mol cat){sup −1} min{sup −1} and maximum hydrogen generation rate of 10,680 L H{sub 2} min{sup −1} (mol cat){sup −1}. Poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles also provide activation energy of 47.4 ± 2.1 kJ/mol for the hydrolysis of ammonia borane. - Highlights: • Ru-Rh@PVP NPs provide a TOF of 386 mol H{sub 2} (mol cat){sup −1} min{sup −1} for hydrolysis of AB. • Maximum HG rate is 9680 L H{sub 2} min{sup −1} (mol cat){sup −1} for the hydrolysis of AB. • Activation energy is 47.4 ± 2.1 kJ mol{sup −1} for the hydrolysis of AB.

  3. Theoretical Research Program on Bio-inspired Inorganic Hydrogen Generating Catalysts and Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Selloni, Annabella; Car, Roberto; Cohen, Morrel H.

    2014-04-17

    In this project, we have successfully designed and characterized a promising biomimetic catalyst/electrode complex, [FeFe]P/FeS2 for producing hydrogen from water. It is comprised of earth-abundant materials and, with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant. The theoretical techniques we have developed and the experience we have gained are broadly applicable for the design and analysis of biomimetic electrochemically active catalysts.

  4. Process for Generation of Hydrogen Gas from Various Feedstocks Using Thermophilic Bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Ooteghem Van, Suellen

    2005-09-13

    A method for producing hydrogen gas is provided comprising selecting a bacteria from the Order Thermotogales, subjecting the bacteria to a feedstock and to a suitable growth environment having an oxygen concentration below the oxygen concentration of water in equilibrium with air; and maintaining the environment at a predetermined pH and at a temperature of at least approximately 45 degrees C. for a time sufficient to allow the bacteria to metabolize the feedstock.

  5. Enhanced hydrogen generation using a saline catholyte in a two chamber microbial electrolysis cell

    KAUST Repository

    Nam, Joo-Youn

    2011-11-01

    High rates of hydrogen gas production were achieved in a two chamber microbial electrolysis cell (MEC) without a catholyte phosphate buffer by using a saline catholyte solution and a cathode constructed around a stainless steel mesh current collector. Using the non-buffered salt solution (68 mM NaCl) produced the highest current density of 131 ± 12 A/m3, hydrogen yield of 3.2 ± 0.3 mol H2/mol acetate, and gas production rate of 1.6 ± 0.2 m3 H2/m 3·d, compared to MECs with catholytes externally sparged with CO2 or containing a phosphate buffer. The salinity of the catholyte achieved a high solution conductivity, and therefore the electrode spacing did not appreciably affect performance. The coulombic efficiency with the cathode placed near the membrane separating the chambers was 83 ± 4%, similar to that obtained with the cathode placed more distant from the membrane (84 ± 4%). Using a carbon cloth cathode instead of the stainless steel mesh cathode did not significantly affect performance, with all reactor configurations producing similar performance in terms of total gas volume, COD removal, rcat and overall energy recovery. These results show MEC performance can be improved by using a saline catholyte without pH control. © 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  6. Novel Hydrogen Bioreactor and Detection Apparatus.

    Science.gov (United States)

    Rollin, Joseph A; Ye, Xinhao; Del Campo, Julia Martin; Adams, Michael W W; Zhang, Y-H Percival

    2016-01-01

    In vitro hydrogen generation represents a clear opportunity for novel bioreactor and system design. Hydrogen, already a globally important commodity chemical, has the potential to become the dominant transportation fuel of the future. Technologies such as in vitro synthetic pathway biotransformation (SyPaB)-the use of more than 10 purified enzymes to catalyze unnatural catabolic pathways-enable the storage of hydrogen in the form of carbohydrates. Biohydrogen production from local carbohydrate resources offers a solution to the most pressing challenges to vehicular and bioenergy uses: small-size distributed production, minimization of CO2 emissions, and potential low cost, driven by high yield and volumetric productivity. In this study, we introduce a novel bioreactor that provides the oxygen-free gas phase necessary for enzymatic hydrogen generation while regulating temperature and reactor volume. A variety of techniques are currently used for laboratory detection of biohydrogen, but the most information is provided by a continuous low-cost hydrogen sensor. Most such systems currently use electrolysis for calibration; here an alternative method, flow calibration, is introduced. This system is further demonstrated here with the conversion of glucose to hydrogen at a high rate, and the production of hydrogen from glucose 6-phosphate at a greatly increased reaction rate, 157 mmol/L/h at 60 °C. PMID:25022362

  7. Novel Hydrogen Bioreactor and Detection Apparatus.

    Science.gov (United States)

    Rollin, Joseph A; Ye, Xinhao; Del Campo, Julia Martin; Adams, Michael W W; Zhang, Y-H Percival

    2016-01-01

    In vitro hydrogen generation represents a clear opportunity for novel bioreactor and system design. Hydrogen, already a globally important commodity chemical, has the potential to become the dominant transportation fuel of the future. Technologies such as in vitro synthetic pathway biotransformation (SyPaB)-the use of more than 10 purified enzymes to catalyze unnatural catabolic pathways-enable the storage of hydrogen in the form of carbohydrates. Biohydrogen production from local carbohydrate resources offers a solution to the most pressing challenges to vehicular and bioenergy uses: small-size distributed production, minimization of CO2 emissions, and potential low cost, driven by high yield and volumetric productivity. In this study, we introduce a novel bioreactor that provides the oxygen-free gas phase necessary for enzymatic hydrogen generation while regulating temperature and reactor volume. A variety of techniques are currently used for laboratory detection of biohydrogen, but the most information is provided by a continuous low-cost hydrogen sensor. Most such systems currently use electrolysis for calibration; here an alternative method, flow calibration, is introduced. This system is further demonstrated here with the conversion of glucose to hydrogen at a high rate, and the production of hydrogen from glucose 6-phosphate at a greatly increased reaction rate, 157 mmol/L/h at 60 °C.

  8. Fractal disperse hydrogen sorption kinetics in spark discharge generated Mg/NbOx and Mg/Pd nanocomposites

    OpenAIRE

    Anastasopol, A.; Pfeiffer, T.V.; Schmidt-Ott, A.; Mulder, F.M.; Eijt, S.W.H.

    2011-01-01

    Isothermal hydrogen desorption of spark discharge generated Mg/NbOx and Mg/Pd metal hydride nanocomposites is consistently described by a kinetic model based on multiple reaction rates, in contrast to the Johnson-Mehl-Avrami-Kolmogorov [M. Avrami, J. Phys. Chem. 9, 177 (1941); W. A. Johnson and R. F. Mehl, Trans. Am. Inst. Min., Metal. Eng. 135, 416 (1939); A. N. Kolmogorov, Izv. Akad. Nauk SSSR, Ser. Mat. 3, 355 (1937); F. Liu, F. Sommer, C. Bos, and E. J. Mittemeijer, Int. Mat. Rev. 52, 193...

  9. Control of Hydrogen Photoproduction by the Proton Gradient Generated by Cyclic Electron Flow in Chlamydomonas reinhardtii[W

    Science.gov (United States)

    Tolleter, Dimitri; Ghysels, Bart; Alric, Jean; Petroutsos, Dimitris; Tolstygina, Irina; Krawietz, Danuta; Happe, Thomas; Auroy, Pascaline; Adriano, Jean-Marc; Beyly, Audrey; Cuiné, Stéphan; Plet, Julie; Reiter, Ilja M.; Genty, Bernard; Cournac, Laurent; Hippler, Michael; Peltier, Gilles

    2011-01-01

    Hydrogen photoproduction by eukaryotic microalgae results from a connection between the photosynthetic electron transport chain and a plastidial hydrogenase. Algal H2 production is a transitory phenomenon under most natural conditions, often viewed as a safety valve protecting the photosynthetic electron transport chain from overreduction. From the colony screening of an insertion mutant library of the unicellular green alga Chlamydomonas reinhardtii based on the analysis of dark-light chlorophyll fluorescence transients, we isolated a mutant impaired in cyclic electron flow around photosystem I (CEF) due to a defect in the Proton Gradient Regulation Like1 (PGRL1) protein. Under aerobiosis, nonphotochemical quenching of fluorescence (NPQ) is strongly decreased in pgrl1. Under anaerobiosis, H2 photoproduction is strongly enhanced in the pgrl1 mutant, both during short-term and long-term measurements (in conditions of sulfur deprivation). Based on the light dependence of NPQ and hydrogen production, as well as on the enhanced hydrogen production observed in the wild-type strain in the presence of the uncoupling agent carbonyl cyanide p-trifluoromethoxyphenylhydrazone, we conclude that the proton gradient generated by CEF provokes a strong inhibition of electron supply to the hydrogenase in the wild-type strain, which is released in the pgrl1 mutant. Regulation of the trans-thylakoidal proton gradient by monitoring pgrl1 expression opens new perspectives toward reprogramming the cellular metabolism of microalgae for enhanced H2 production. PMID:21764992

  10. Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by Gold(I) Complexes%金(I)配合物催化乙烯加氢的反应机理

    Institute of Scientific and Technical Information of China (English)

    仇毅翔; 万明达; 陈先阳; 王曙光

    2013-01-01

    The reaction mechanisms of ethylene hydrogenation catalyzed by Au(I) complexes AuX (X=F, Cl, Br, I) and AuPR3+ (R = F, Cl, Br, I, H, Me, Ph) were investigated using density functional theory at the B3LYP level. The calculated results indicated that Au(I) complexes were effective catalysts in the hydrogenation of ethylene. AuPR3+ showed higher catalytic activity than AuX and the effect of changing the electron donating or withdrawing ability of the ligand on catalytic activity was large. Natural bond orbital analysis indicated that the interactions between the Au(I) complex and H2/C2H4 not only weakened the H―H/C=C bond strength, but also decreased the energy of the σ*H ― H、π*C=C orbital level. As a result, the energy differences of πC=C-σ*H ― H/σH ― H-π*C=C decreased, and ethylene hydrogenation was facilitated. A linear correlation was observed between the activation energies and πC=C-σ*H ― H/σH ― H-π*C=C. The more an Au(I) complex affected the σ*H―H/π*C=C orbital levels, the higher its catalytic activity.%  采用密度泛函理论B3LYP方法,对两类金(I)配合物AuX (X=F, Cl, Br, I)和AuPR3+(R=F, Cl, Br, I, H, Me, Ph)催化C2H4加氢反应的机理进行了理论研究.计算显示Au(I)配合物对C2H4氢化具有较好的催化效果,其作用下的加氢反应存在“活化H―H键后再与C2H4反应”和“活化C=C键后再与H2反应”两种途径,前者的活化能较后者低90-120 kJ·mol-1,因而具有明显的能量优势.研究表明AuPR3+的催化能力明显强于AuX.此外, X/PR3基团供、吸电子能力的变化对配合物的催化能力也具有较为显著的影响.电子结构分析显示Au(I)配合物在C2H4加氢反应中不仅能够削弱 H―H、C=C 键的强度,还使 H2σ*H―H、C2H4π*C=C轨道能级下降,从而缩小了πC=C-σ*H―H或σH―H-π*C=C轨道间的能级差,促进了 C2H4-H2反应中的电子离域,从而降低禁阻反应发生的难度.σ*H―H、π*C=C轨道能级改变量与

  11. Production of HBR from bromine and steam for off-peak electrolytic hydrogen generation

    Energy Technology Data Exchange (ETDEWEB)

    Schlief, R.E.; Hanrahan, R.J.; Stoy, M.A. [Univ. of Florida, Gainesville, FL (United States)] [and others

    1995-09-01

    Progress is reported on the development of a renewable energy source based solar-electrolytic system for production of hydrogen and oxygen. It employs water, bromine, solar energy and supplemental electrical power. The concept is being developed by Solar Reactor Technologies, Inc., (SRT), with the U.S. Department of Energy (DOE). An overview of the nature and objectives of this program is provided here, and technical progress made during the first (three-month) performance period of the Phase I work effort is reported. The SRT concept entails (1) absorption of concentrated solar radiation by bromine vapor Br{sub 2(g)} in a high-temperature reactor producing Br{sub (g)} atoms, (2) reaction of Br{sub (g)} with water yielding hydrogen bromide (HBr), and (3) electrolysis of stored hydrogen bromide for production of H{sub 2(g)} and recovery of Br{sub 2(I)}. Incorporation of solar radiation in the primary photochemical step (1) reduces by 50 - 70% the electrical power required to split water. The SRT concept is very attractive from an economic viewpoint as well. The reversible fuel cell, employed in the SRT electrolysis concept is capitalized via its use in load leveling by the utility. A 1 kW solar reactor was designed and constructed during the first three-month performance period by SRT personnel at the University of Florida, Gainesville. It was employed in taking survey data of the reaction between bromine and steam at temperatures between 900 and 1300 K. This reaction was run under purely thermal conditions, i.e. in the absence of solar photons. The experimental data are reported and interpreted employing concomitant thermodynamic calculations. The anticipated improvement is discussed briefly as well as the effect of a photochemical boost to the reaction. The amount of this enhancement will be studied in the next three month performance period.

  12. Dye-sensitized Pt@TiO2 core–shell nanostructures for the efficient photocatalytic generation of hydrogen

    Directory of Open Access Journals (Sweden)

    Jun Fang

    2014-03-01

    Full Text Available Pt@TiO2 core–shell nanostructures were prepared through a hydrothermal method. The dye-sensitization of these Pt@TiO2 core–shell structures allows for a high photocatalytic activity for the generation of hydrogen from proton reduction under visible-light irradiation. When the dyes and TiO2 were co-excited through the combination of two irradiation beams with different wavelengths, a synergic effect was observed, which led to a greatly enhanced H2 generation yield. This is attributed to the rational spatial distribution of the three components (dye, TiO2, Pt, and the vectored transport of photogenerated electrons from the dye to the Pt particles via the TiO2 particle bridge.

  13. Interaction of gas phase atomic hydrogen with Pt(111):Direct evidence for the formation of bulk hydrogen species

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Employing hot tungsten filament to thermal dissociate molecular hydrogen,we generated gas phase atomic hydrogen under ultra-high vacuum(UHV)conditions and investigated its interaction with Pt(111) surface.Thermal desorption spectroscopy(TDS)results demonstrate that adsorption of molecular hy- drogen on Pt(111)forms surface Had species whereas adsorption of atomic hydrogen forms not only surface Had species but also bulk Had species.Bulk Had species is more thermal-unstable than surface Had species on Pt(111),suggesting that bulk Had species is more energetic.This kind of weakly- adsorbed bulk Had species might be the active hydrogen species in the Pt-catalyzed hydrogenation reactions.

  14. Room-Temperature and Aqueous-Phase Synthesis of Plasmonic Molybdenum Oxide Nanoparticles for Visible-Light-Enhanced Hydrogen Generation.

    Science.gov (United States)

    Shi, Jiayuan; Kuwahara, Yasutaka; Wen, Meicheng; Navlani-García, Miriam; Mori, Kohsuke; An, Taicheng; Yamashita, Hiromi

    2016-09-01

    A straightforward aqueous synthesis of MoO3-x nanoparticles at room temperature was developed by using (NH4 )6 Mo7 O24 ⋅4 H2 O and MoCl5 as precursors in the absence of reductants, inert gas, and organic solvents. SEM and TEM images indicate the as-prepared products are nanoparticles with diameters of 90-180 nm. The diffuse reflectance UV-visible-near-IR spectra of the samples indicate localized surface plasmon resonance (LSPR) properties generated by the introduction of oxygen vacancies. Owing to its strong plasmonic absorption in the visible-light and near-infrared region, such nanostructures exhibit an enhancement of activity toward visible-light catalytic hydrogen generation. MoO3-x nanoparticles synthesized with a molar ratio of Mo(VI) /Mo(V) 1:1 show the highest yield of H2 evolution. The cycling catalytic performance has been investigated to indicate the structural and chemical stability of the as-prepared plasmonic MoO3-x nanoparticles, which reveals its potential application in visible-light catalytic hydrogen production. PMID:27555123

  15. Significant improvements in InGaN/GaN nano-photoelectrodes for hydrogen generation by structure and polarization optimization.

    Science.gov (United States)

    Tao, Tao; Zhi, Ting; Liu, Bin; Li, Mingxue; Zhuang, Zhe; Dai, Jiangping; Li, Yi; Jiang, Fulong; Luo, Wenjun; Xie, Zili; Chen, Dunjun; Chen, Peng; Li, Zhaosheng; Zou, Zhigang; Zhang, Rong; Zheng, Youdou

    2016-02-08

    The photoelectrodes based on III-nitride semiconductors with high energy conversion efficiency especially for those self-driven ones are greatly desirable for hydrogen generation. In this study, highly ordered InGaN/GaN multiple-quantum-well nanorod-based photoelectrodes have been fabricated by a soft UV-curing nano-imprint lithography and a top-down etching technique, which improve the incident photon conversion efficiency (IPCE) from 16% (planar structure) to 42% (@ wavelength = 400 nm). More significantly, the turn-on voltage is reduced low to -0.6 V, which indicates the possibility of achieving self-driven. Furthermore, SiO2/Si3N4 dielectric distributed Bragg reflectors are employed to further improve the IPCE up to 60%. And the photocurrent (@ 1.1 V) is enhanced from 0.37 mA/cm(2) (original planar structure) to 1.5 mA/cm(2). These improvements may accelerate the possible applications for hydrogen generation with high energy-efficiency.

  16. Hanford waste vitrification plant hydrogen generation study: Preliminary evaluation of alternatives to formic acid

    Energy Technology Data Exchange (ETDEWEB)

    King, R.B.; Bhattacharyya, N.K.; Kumar, V.

    1996-02-01

    Oxalic, glyoxylic, glycolic, malonic, pyruvic, lactic, levulinic, and citric acids as well as glycine have been evaluated as possible substitutes for formic acid in the preparation of feed for the Hanford waste vitrification plant using a non-radioactive feed stimulant UGA-12M1 containing substantial amounts of aluminum and iron oxides as well as nitrate and nitrite at 90C in the presence of hydrated rhodium trichloride. Unlike formic acid none of these carboxylic acids liberate hydrogen under these conditions and only malonic and citric acids form ammonia. Glyoxylic, glycolic, malonic, pyruvic, lactic, levulinic, and citric acids all appear to have significant reducing properties under the reaction conditions of interest as indicated by the observation of appreciable amounts of N{sub 2}O as a reduction product of,nitrite or, less likely, nitrate at 90C. Glyoxylic, pyruvic, and malonic acids all appear to be unstable towards decarboxylation at 90C in the presence of Al(OH){sub 3}. Among the carboxylic acids investigated in this study the {alpha}-hydroxycarboxylic acids glycolic and lactic acids appear to be the most interesting potential substitutes for formic acid in the feed preparation for the vitrification plant because of their failure to produce hydrogen or ammonia or to undergo decarboxylation under the reaction conditions although they exhibit some reducing properties in feed stimulant experiments.

  17. Catalytic hydro desulphurization study of heavy petroleum residue through in situ generated hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Shakirullah, Mohammad; Ahmad, Imtiaz; Ishaq, Mohammad; Ahmad, Waqas [Institute of Chemical Sciences, N.W.F.P., University of Peshawar, 25120 Peshawar (Pakistan)

    2010-05-15

    Hydrodesulphurization of heavy residue was carried out using various catalysts in the presence of co-reactants as the internal sources of hydrogen. Reactions were carried out in a micro autoclave at 320 C and 10 kg f/cm{sup 2} pressure inert atmosphere of N{sub 2} for 3 h reaction time. Tetralin, propane, methanol, ethylene glycol and formic acid were separately used as co-reactants as hydrogen donors. Among the solvents studied, methanol gave the highest hydrodesulphurization yield (52%). The reaction was then carried out in the presence of various catalysts to view the influence of each individual catalyst on the desulphurization yield under the same conditions of pressure and temperature. The catalysts used were Mo-Montmorillonite, Co-Montmorillonite, nickel oxide (NiO), cadmium oxide (CdO), Zn-ZSM5, kaolin and montmorillonite clays. The results show that all the catalysts exhibited desulphurization activity. In case of Mo-Montmorillonite and Co-Montmorillonite charges, the desulfurization yields of 63% and 46% were obtained, respectively. NiO, CdO, Zn-ZSM5, kaolin and montmorillonite clays gave desulphurization yields of 54%, 50%, 56%, 20% and 36%, respectively. The desulphurization activities of Mo-Montmorillonite and Co-Montmorillonite were compared with other catalysts used. The results show that Mo-Montmorillonite gave the highest hydrodesulphurization yield. FTIR studies also confirmed the hydrodesulphurization efficiency of the Mo-Montmorillonite. (author)

  18. Global Assessment of Hydrogen Technologies – Task 5 Report Use of Fuel Cell Technology in Electric Power Generation

    Energy Technology Data Exchange (ETDEWEB)

    Fouad, Fouad H.; Peters, Robert W.; Sisiopiku, Virginia P.; Sullivan Andrew J.; Ahluwalia, Rajesh K.

    2007-12-01

    The purpose of this work was to assess the performance of high temperature membranes and observe the impact of different parameters, such as water-to-carbon ratio, carbon formation, hydrogen formation, efficiencies, methane formation, fuel and oxidant utilization, sulfur reduction, and the thermal efficiency/electrical efficiency relationship, on fuel cell performance. A 250 KW PEM fuel cell model was simulated [in conjunction with Argonne National Laboratory (ANL) with the help of the fuel cell computer software model (GCtool)] which would be used to produce power of 250 kW and also produce steam at 120oC that can be used for industrial applications. The performance of the system was examined by estimating the various electrical and thermal efficiencies achievable, and by assessing the effect of supply water temperature, process water temperature, and pressure on thermal performance. It was concluded that increasing the fuel utilization increases the electrical efficiency but decreases the thermal efficiency. The electrical and thermal efficiencies are optimum at ~85% fuel utilization. The low temperature membrane (70oC) is unsuitable for generating high-grade heat suitable for useful cogeneration. The high temperature fuel cells are capable of producing steam through 280oC that can be utilized for industrial applications. Increasing the supply water temperature reduces the efficiency of the radiator. Increasing the supply water temperature beyond the dew point temperature decreases the thermal efficiency with the corresponding decrease in high-grade heat utilization. Increasing the steam pressure decreases the thermal efficiency. The environmental impacts of fuel cell use depend upon the source of the hydrogen rich fuel used. By using pure hydrogen, fuel cells have virtually no emissions except water. Hydrogen is rarely used due to problems with storage and transportation, but in the future, the growth of a “solar hydrogen economy” has been projected

  19. Hydrogen sulfide is endogenously generated in rat skeletal muscle and exerts a protective effect against oxidative stress

    Institute of Scientific and Technical Information of China (English)

    DU Jian-tong; LI Wei; YANG Jin-yan; TANG Chao-shu; LI Qi; JIN Hong-fang

    2013-01-01

    Background Skeletal muscle has recently been recognized as an endocrine organ that can express,synthesize and secrete a variety of bioactive molecules which exert significant regulatory effects.Hydrogen sulfide (H2S) is endogenously produced in mammalian tissues and participates in a number of physiological and pathophysiological processes.We aimed to verify whether H2S could be endogenously generated and released by rat skeletal muscle,and determine the biological effects of H2S in rat skeletal muscle.Methods The study was divided into two parts:detection of endogenous H2S generation and release in rat skeletal muscle and determination of antioxidative activity of skeletal muscle-derived H2S.H2S content and production in tissues were detected by sensitive sulfur electrode method.The expressions of H2S producing enzymes cystathionine β-synthase,cystathionine Y-lyase and mercaptopyruvate sulfurtransferase were detected by real-time PCR and western blotting and their tissue distributions were observed by immunohistochemical and immunofluorescent analysis.Rat skeletal muscular ischemia-reperfusion (I-R) injury model was created and evaluated by histological analysis under microscope.The malondialdehyde (MDA) contents,hydrogen peroxide levels,superoxide anion and superoxide dismutase (SOD) activities were detected using spectrophotometer.Results H2S could be endogenously generated and released by skeletal muscle of Sprague-Dawley rats (H2S content:(2.06±0.43) nmol/mg; H2S production:(0.17±0.06) nmol.min-1·mg-1).Gene and protein expressions of the three H2S producing enzymes were detected in skeletal muscle,as well as the liver and kidney.Endogenous H2S content and production were decreased in skeletal muscles of rats with I-R skeletal muscle injury (P <0.05).Furthermore,H2S significantly protected rat skeletal muscle against I-R injury and resulted in decreased MDA content,reduced hydrogen peroxide and superoxide anion levels,but increased SOD activity and

  20. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase.

    Science.gov (United States)

    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A

    2016-07-13

    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  1. 5 kW DC/DC converter for hydrogen generation from photovoltaic sources

    Energy Technology Data Exchange (ETDEWEB)

    Garrigos, A.; Blanes, J.M.; Carrasco, J.A.; Lizan, J.L. [Area de Tecnologia Electronica, Universidad Miguel Hernandez de Elche, Avda. de la Universidad s/n, 03202 Elche, Alicante (Spain); Beneito, R. [AIJU, Avda. de la Industria 23, 03440 Ibi, Alicante (Spain); Molina, J.A. [Grupo SITEC, Calle Cadiz 38, Poligono Industrial L' Alfac III, 03440 Ibi, Alicante (Spain)

    2010-06-15

    This paper covers the design of a DC-DC power converter aimed for hydrogen production from photovoltaic sources. Power conditioning for such application is usually driven by different constraints: high step-down conversion ratio is required if the input voltage of such equipment has to be compatible with photovoltaic sources that are connected to grid-connected inverters; galvanic isolation; high efficiency and low mass. Taking into account those factors, this work proposes a push-pull DC/DC converter for power levels up to 5 kW. The operation and features of the converter are presented and analyzed. Design guidelines are suggested and experimental validation is also given. (author)

  2. ASSESSMENT OF THE POTENTIAL FOR HYDROGEN GENERATION DURING GROUTING OPERATIONS IN THE R AND P REACTOR VESSELS

    Energy Technology Data Exchange (ETDEWEB)

    Wiersma, B.

    2010-05-24

    operations in the R-reactor vessel is low for the Portland cement. Alternatively, if the grout fill rate is less than 0.5 inch/min and the grout is maintained at a temperature of 80 C, the risk is again low. Although these calculations are conservative, there are some measures that may be taken to further minimize the potential for hydrogen evolution. (1) Minimize the temperature of the grout as much as practical. Lower temperatures will mean lower hydrogen generation rates. For P-reactor, grout temperatures less than 100 C should provide an adequate safety margin for the pH 8 and pH 10.4 grout formulations. For R-reactor, grout temperatures less than 70 C or 80 C will provide an adequate safety margin for the Portland cement. The other grout formulations are also viable options for R-reactor. (2) Minimize the grout fill rate as much as practical. Lowering the fill rate takes advantage of passivation of the aluminum components and hence lower hydrogen generation rates. For P-reactor, fill rates that are less than 2 inches/min for the ceramicrete and the silica fume grouts will reduce the chance of significant hydrogen accumulation. For R-reactor, fill rates less than 1 inch/min will again minimize the risk of hydrogen accumulation. (3) Ventilate the building as much as practical (e.g., leave doors open) to further disperse hydrogen. The volumetric hydrogen generation rates in the P-reactor vessel, however, are low for the pH 8 and pH 10.4 grout, (i.e., less than 0.97 ft{sup 3}/min). If further walk-down inspections of the reactor vessels suggest an increase in the actual areal density of aluminum, the calculations should be re-visited.

  3. Effect of three disinfectants (chlorhexidine, sodium hypochlorite and hydrogen peroxide on the microleakage of 7th generation bonding agents

    Directory of Open Access Journals (Sweden)

    Salari Behzad

    2013-10-01

    Full Text Available   Background and Aims : The aim of this study was to evaluate the effect of chlorhexidin 2%, sodium hypochlorite 2.5% and hydrogen peroxide 3% as three effective and regular disinfectants on the microleakage of 7th generation bonding agents in vitro.   Materials and Methods: 45 extracted molar teeth without carries were collected and disinfected. On buccal and lingual aspects of these teeth conventional class V cavity preparation were done (90 cavities, then randomly divided to 4 groups, three of them had 10 teeth (20 cavities and one of them had 5 teeth (10 cavities as control group. Cavities in each experimental group prepared with one of the disinfectants and then 7th generation bonding (Optibond all in one, kerr was used as noted by manufacturer, then cavities filled with composite and polished. Bonding agent was used without our previous disinfectants manipulation in control group. Specimens were thermocycled with 1000 thermal cycles between 5 and 55 0 C each for 30 seconds and then immersed in the methylene blue 5%, then sectioned mesiodistally and investigated for microleakage under stereomicroscope (Olympus, Japan. Data were analyzed using Kruskal-Wallis and Wilcoxon mean rank tests.   Results: Despite the lower mean rank values for the untreated group at both occlusal and gingival aspects, the Kruskal-Wallis procedure (α=0.05 showed that the treatment factor did not significantly affect the mean rank values neither in occlusal (P=0.12 nor in gingival (P=0.39 part of cavities.   Conclusion: According to the results of this study, antimicrobial agents such as chlorhexidine 2%, sodium hypochloride 2.5% and hydrogen peroxide 3% can be used perior to 7th generation dentin bonding agent(Optibond all in one, kerr without much concern.

  4. Methane formation from CaCO3 reduction catalyzed by high pressure

    Institute of Scientific and Technical Information of China (English)

    Jin Yang Chen; Lu Jiang Jin; Jun Ping Dong; Hai Fei Zheng; Gui Yang Liu

    2008-01-01

    Under high pressures of several giga-pascals using hydrothermal diamond anvil cell,methane generated directly from CaCO3 reduction in gold-lined chamber is in situ measured by Raman spectroscopy at the temperature of 550 ℃.The reducing agents include FeO,SiO and natural fayalite (Fe2SiO4),and the resource of hydrogen are water and natural serpentine (Mg3Si2O5(OH)4).The study demonstrates the existence of abiogenic formation of methane under high pressures in the Earth's interior and that the application of high pressure to catalyze multicomponent reactions is a very promising method.

  5. Photocatalytic hydrogen generation of Pt-Sr(Zr1-xYx)03-δ-Ti02 heterojunction under the irradiation of simulated sunlight

    Institute of Scientific and Technical Information of China (English)

    Jianhui YAN; Qiang LIU; Luxiong GUAN; Feng LIANG; Haojie GU

    2009-01-01

    The Pt-Sr(Zr1-xYx)O3-δ-Ti02 (Pt-SZYT) heterojunction photocatalysts were prepared by a photodepo-sition method. The composite particles were characterized by XRD, SEM, UV-Vis DRS, and PL techniques. Photocatalytic hydrogen generation in H2C2O4 aqueous solution under the irradiation of simulated sunlight was used as a probe reaction to evaluate the photocatalytic activity of the photocatalysts. The effects of the content of Pt loading and the concentration of oxalic acid on the photocatalytic activity of the catalyst were discussed. The continuous photocatalytic activity of the Pt-SZYT and the relationship between PL intensity and hydrogen generation were also discussed. The results show that Pt-SZYT catalysts had high photocatalytic activity of hydrogen generation. The content of Pt loading and the concentration of oxalic acid have important influence on the photocatalytic hydrogen generation. The optimal loading content of platinum was 0.90 mass%. Under this condition, the average rate of photocatalytic hydrogen generation was 1.68mmol-h ' when the concentration of oxalic acid was 50mmol-L"'. The higher the photocatalytic activity, the weaker the PL intensity, which was demonstrated by the analysis of PL spectra.

  6. Sacrificial hydrogen generation from aqueous triethanolamine with Eosin Y-sensitized Pt/TiO2 photocatalyst in UV, visible and solar light irradiation.

    Science.gov (United States)

    Chowdhury, Pankaj; Gomaa, Hassan; Ray, Ajay K

    2015-02-01

    In this paper, we have studied Eosin Y-sensitized sacrificial hydrogen generation with triethanolamine as electron donor in UV, visible, and solar light irradiation. Aeroxide TiO2 was loaded with platinum metal via solar photo-deposition method to reduce the electron hole recombination process. Photocatalytic sacrificial hydrogen generation was influenced by several factors such as platinum loading (wt%) on TiO2, solution pH, Eosin Y to Pt/TiO2 mass ratio, triethanolamine concentration, and light (UV, visible and solar) intensities. Detailed reaction mechanisms in visible and solar light irradiation were established. Oxidation of triethanolamine and formaldehyde formation was correlated with hydrogen generation in both visible and solar lights. Hydrogen generation kinetics followed a Langmuir-type isotherm with reaction rate constant and adsorption constant of 6.77×10(-6) mol min(-1) and 14.45 M(-1), respectively. Sacrificial hydrogen generation and charge recombination processes were studied as a function of light intensities. Apparent quantum yields (QYs) were compared for UV, visible, and solar light at four different light intensities. Highest QYs were attained at lower light intensity because of trivial charge recombination. At 30 mW cm(-2) we achieved QYs of 10.82%, 12.23% and 11.33% in UV, visible and solar light respectively.

  7. Polyacrylonitrile Fibers Anchored Cobalt/Graphene Sheet Nanocomposite: A Low-Cost, High-Performance and Reusable Catalyst for Hydrogen Generation.

    Science.gov (United States)

    Zhang, Fei; Huang, Guoji; Hou, Chengyi; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang

    2016-06-01

    Cobalt and its composites are known to be active and inexpensive catalysts in sodium borohydride (NaBH4) hydrolysis to generate clean and renewable hydrogen energy. A novel fiber catalyst, cobalt/graphene sheet nanocomposite anchored on polyacrylonitrile fibers (Co/GRs-PANFs), which can be easily recycled and used in any reactor with different shapes, were synthesized by anchoring cobalt/graphene (Co/GRs) on polyacrylonitrile fibers coated with graphene (GRs-PANFs) at low temperature. The unique structure design effectively prevents the inter-sheet restacking of Co/GRs and fully exploits the large surface area of novel hybrid material for generate hydrogen. And the extra electron transfer path supplied by GRs on the surface of GRs-PANFs can also enhance their catalysis performances. The catalytic activity of the catalyst was investigated by the hydrolysis of NaBH4 in aqueous solution with GRs-PANFs. GRs powders and Co powders were used as control groups. It was found that both GRs and fiber contributed to the hydrogen generation rate of Co/GRs-PANFs (3222 mL x min(-1) x g(-1)), which is much higher than that of cobalt powders (915 mL x min(-1) x g(-1)) and Co/GRs (995 mL x min(-1) x g(-1)). The improved hydrogen generation rate, low cost and uncomplicated recycling make the Co/GRs-PANFs promising candidate as catalysts for hydrogen generation. PMID:27427607

  8. Generation and Retention of Helium and Hydrogen in Austenitic Steels Irradiated in a Variety of LWR and Test Reactor Spectral Environments

    Energy Technology Data Exchange (ETDEWEB)

    Garner, Francis A.; Oliver, Brian M.; Greenwood, Lawrence R.; Edwards, Danny J.; Bruemmer, Stephen M.; Grossbeck, Martin L.

    2002-03-31

    In fission and fusion reactor environments stainless steels generate significant amounts of helium and hydrogen by transmutation. The primary sources of helium are boron and nickel, interacting with both fast and especially thermal neutrons. Hydrogen arises primarily from fast neutron reactions, but is also introduced into steels at often much higher levels by other environmental processes. Although essentially all of the helium is retained in the steel, it is commonly assumed that most of the hydrogen is not retained. It now appears that under some circumstances, significant levels of hydrogen can be retained, especially when helium-nucleated cavities become a significant part of the microstructure. A variety of stainless steel specimens have been examined from various test reactors, PWRs and BWRs. These specimens were exposed to a wide range of neutron spectra with different thermal/fast neutron ratios. Pure nickel and pure iron have also been examined. It is shown that all major features of the retention of helium and hydrogen can be explained in terms of the composition, thermal/fast neutron ratio and the presence or absence of helium-nucleated cavities. In some cases, the hydrogen retention is very large and can exceed that generated by transmutation, with the additional hydrogen arising from either environmental sources and/or previously unidentified radioisotope sources that may come into operation at high neutron exposures.

  9. Photocatalytic water splitting for hydrogen generation on cubic, orthorhombic, and tetragonal KNbO3 microcubes

    Science.gov (United States)

    Zhang, Tingting; Zhao, Kun; Yu, Jiaguo; Jin, Jian; Qi, Yang; Li, Huiquan; Hou, Xinjuan; Liu, Gang

    2013-08-01

    Potassium niobate (KNbO3) microcubes with orthorhombic and tetragonal phases were hydrothermally prepared and characterized by powder X-ray diffraction, nitrogen adsorption-desorption, micro-Raman spectroscopy, Fourier transform infrared spectroscopy, diffuse reflectance UV-visible spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The photoreactivity of the as-prepared KNbO3 samples was evaluated regarding the hydrogen evolution from aqueous methanol under UV, and the results were compared with that of cubic KNbO3 microcubes. The photocatalytic reactivity was shown to be phase-dependent, following the order cubic > orthorhombic > tetragonal. Insight into the phase-dependent photocatalytic properties was gained by first-principles density functional calculations. The best photocatalytic performance of cubic KNbO3 is ascribed to it having the highest symmetry in the bulk structure and associated unique electronic structure. Further, the surface electronic structure plays a key role leading to the discrepancy in photoreactivity between orthorhombic and tetragonal KNbO3. The results from this study are potentially applicable to a range of perovskite-type mixed metal oxides useful in water splitting as well as other areas of heterogeneous photocatalysis.Potassium niobate (KNbO3) microcubes with orthorhombic and tetragonal phases were hydrothermally prepared and characterized by powder X-ray diffraction, nitrogen adsorption-desorption, micro-Raman spectroscopy, Fourier transform infrared spectroscopy, diffuse reflectance UV-visible spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The photoreactivity of the as-prepared KNbO3 samples was evaluated regarding the hydrogen evolution from aqueous methanol under UV, and the results were compared with that of cubic KNbO3 microcubes. The photocatalytic reactivity was

  10. Hydrogen peroxide is generated during the very early stages of aggregation of the amyloid peptides implicated in Alzheimer disease and familial British dementia.

    Science.gov (United States)

    Tabner, Brian J; El-Agnaf, Omar M A; Turnbull, Stuart; German, Matthew J; Paleologou, Katerina E; Hayashi, Yoshihito; Cooper, Leanne J; Fullwood, Nigel J; Allsop, David

    2005-10-28

    Alzheimer disease and familial British dementia are neurodegenerative diseases that are characterized by the presence of numerous amyloid plaques in the brain. These lesions contain fibrillar deposits of the beta-amyloid peptide (Abeta) and the British dementia peptide (ABri), respectively. Both peptides are toxic to cells in culture, and there is increasing evidence that early "soluble oligomers" are the toxic entity rather than mature amyloid fibrils. The molecular mechanisms responsible for this toxicity are not clear, but in the case of Abeta, one prominent hypothesis is that the peptide can induce oxidative damage via the formation of hydrogen peroxide. We have developed a reliable method, employing electron spin resonance spectroscopy in conjunction with the spin-trapping technique, to detect any hydrogen peroxide generated during the incubation of Abeta and other amyloidogenic peptides. Here, we monitored levels of hydrogen peroxide accumulation during different stages of aggregation of Abeta-(1-40) and ABri and found that in both cases it was generated as a short "burst" early on in the aggregation process. Ultrastructural studies with both peptides revealed that structures resembling "soluble oligomers" or "protofibrils" were present during this early phase of hydrogen peroxide formation. Mature amyloid fibrils derived from Abeta-(1-40) did not generate hydrogen peroxide. We conclude that hydrogen peroxide formation during the early stages of protein aggregation may be a common mechanism of cell death in these (and possibly other) neurodegenerative diseases.

  11. Comparison of hydrogen generation for TVSM and TVSA fuel assemblies for water water energy reactor (VVER)-1000

    Energy Technology Data Exchange (ETDEWEB)

    Stefanova, A.E. [Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, Tzarigradsko Shaussee 72, Sofia 1784 (Bulgaria)], E-mail: antoanet@inrne.bas.bg; Groudev, P.P. [Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, Tzarigradsko Shaussee 72, Sofia 1784 (Bulgaria)], E-mail: pavlinpg@inrne.bas.bg; Atanasova, B.P. [Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, Tzarigradsko Shaussee 72, Sofia 1784 (Bulgaria)], E-mail: b_atanasova@inrne.bas.bg

    2009-01-15

    This paper presents the results received during investigation of hydrogen generation for both types fuel assemblies-the old modernistic type of fuel assemblies (TVSM) and recently installed new one alternative type of fuel assemblies (TVSA) in case of severe accident. There are some differences between both types FAs. They have different geometry as well as different burnable poisons. To investigate behavior of new fuel assemblies during the severe conditions it have been performed comparison of fuel behavior of old type TVSM fuel assembly to new one TVSA. To perform this investigation it has been used MELCOR 'input model' for Kozloduy Nuclear Power Plant (KNPP) VVER 1000. The model was developed by Institute for Nuclear Research and Nuclear Energy-Bulgarian Academy of Sciences (INRNE-BAS) for investigation of severe accident scenarios and Probabilistic Safety Analyses (PSA) level 2. The model provides a significant analytical capability for the Bulgarian technical specialists, working in the field of the NPP safety, for analysis of core and containment damaged states and the estimation of radionuclides release outside fuel cladding. It was accepted criteria for vessel integrity about hydrogen concentration to be 8%. This criterion was based on the decision of RSK (Germany commission for reactor safety). Generally based on the received results it was made conclusion that using both types of fuel assemblies it was not disturbance safety conditions of NPP.

  12. Zeolite-confined ruthenium(0) nanoclusters catalyst: record catalytic activity, reusability, and lifetime in hydrogen generation from the hydrolysis of sodium borohydride.

    Science.gov (United States)

    Zahmakiran, Mehmet; Ozkar, Saim

    2009-03-01

    Sodium borohydride, NaBH4, has been considered the most attractive hydrogen-storage material for portable fuel cell applications, as it provides a safe and practical means of producing hydrogen. In a recent communication (Zahmakiran, M.; Ozkar, S. Langmuir 2008, 24, 7065), we have reported a record total turnover number (TTON) of 103 200 mol H2/mol Ru and turnover frequency (TOF) up to 33 000 mol H2/mol Ru x h obtained by using intrazeolite ruthenium(0) nanoclusters in the hydrolysis of sodium borohydride. Here we report full details of the kinetic studies on the intrazeolite ruthenium(0) nanoclusters catalyzed hydrolysis of sodium borohydride in both aqueous and basic solutions. Expectedly, the intrazeolite ruthenium(0) nanoclusters show unprecedented catalytic lifetime, TTON = 27 200 mol H2/mol Ru, and TOF up to 4000 mol H2/mol Ru x h in the hydrolysis of sodium borohydride in basic solution (5% wt NaOH) as well. More importantly, the intrazeolite ruthenium(0) nanoclusters are isolable, bottleable, redispersible, and yet catalytically active. They retain 76% or 61% of their initial catalytic activity at the fifth run with a complete release of hydrogen in aqueous and basic medium, respectively. The intrazeolite ruthenium(0) nanoclusters were isolated as black powder and characterized by using a combination of advanced analytical techniques including XRD, HRTEM, TEM-EDX, SEM, XPS, ICP-OES, and N2 adsorption. PMID:19437749

  13. A Visible-Light-Active Heterojunction with Enhanced Photocatalytic Hydrogen Generation.

    Science.gov (United States)

    Adhikari, Shiba P; Hood, Zachary D; More, Karren L; Chen, Vincent W; Lachgar, Abdou

    2016-07-21

    A visible-light-active carbon nitride (CN)/strontium pyroniobate (SNO) heterojunction photocatalyst was fabricated by deposition of CN over hydrothermally synthesized SNO nanoplates by a simple thermal decomposition process. The microscopic study revealed that nanosheets of CN were anchored to the surface of SNO resulting in an intimate contact between the two semiconductors. Diffuse reflectance UV/Vis spectra show that the resulting CN/SNO heterojunction possesses intense absorption in the visible region. The structural and spectral properties endowed the CN/SNO heterojunction with remarkably enhanced photocatalytic activity. Specifically, the photocatalytic hydrogen evolution rate per mole of CN was found to be 11 times higher for the CN/SNO composite compared to pristine CN. The results clearly show that the composite photocatalyst not only extends the light absorption range of SNO but also restricts photogenerated charge-carrier recombination, resulting in significant enhancement in photocatalytic activity compared to pristine CN. The relative band positions of the composite allow the photogenerated electrons in the conduction band of CN to migrate to that of SNO. This kind of charge migration and separation leads to the reduction in the overall recombination rate of photogenerated charge carriers, which is regarded as one of the key factors for the enhanced activity. A plausible mechanism for the enhanced photocatalytic activity of the heterostructured composite is proposed based on observed activity, photoluminescence, time-resolved fluorescence emission decay, electrochemical impedance spectroscopy, and band position calculations. PMID:27282318

  14. Hydrogen Generation from Catalytic Steam Reforming of Acetic Acid by Ni/Attapulgite Catalysts

    Directory of Open Access Journals (Sweden)

    Yishuang Wang

    2016-11-01

    Full Text Available In this research, catalytic steam reforming of acetic acid derived from the aqueous portion of bio-oil for hydrogen production was investigated using different Ni/ATC (Attapulgite Clay catalysts prepared by precipitation, impregnation and mechanical blending methods. The fresh and reduced catalysts were characterized by XRD, N2 adsorption–desorption, TEM and temperature program reduction (H2-TPR. The comprehensive results demonstrated that the interaction between active metallic Ni and ATC carrier was significantly improved in Ni/ATC catalyst prepared by precipitation method, from which the mean of Ni particle size was the smallest (~13 nm, resulting in the highest metal dispersion (7.5%. The catalytic performance of the catalysts was evaluated by the process of steam reforming of acetic acid in a fixed-bed reactor under atmospheric pressure at two different temperatures: 550 °C and 650 °C. The test results showed the Ni/ATC prepared by way of precipitation method (PM-Ni/ATC achieved the highest H2 yield of ~82% and a little lower acetic acid conversion efficiency of ~85% than that of Ni/ATC prepared by way of impregnation method (IM-Ni/ATC (~95%. In addition, the deactivation catalysts after reaction for 4 h were analyzed by XRD, TGA-DTG and TEM, which demonstrated the catalyst deactivation was not caused by the amount of carbon deposition, but owed to the significant agglomeration and sintering of Ni particles in the carrier.

  15. CoP nanosheet assembly grown on carbon cloth: A highly efficient electrocatalyst for hydrogen generation

    KAUST Repository

    Yang, Xiulin

    2015-07-01

    There exists a strong demand to replace expensive noble metal catalysts with cheap metal sulfides or phosphides for hydrogen evolution reaction (HER). Recently metal phosphides such as NixP, FeP and CoP have been considered as promising candidates to replace Pt cathodes. Here we report that the nanocrystalline CoP nanosheet assembly on carbon cloth can be formed by a two-step process: electrochemical deposition of Co species followed by gas phase phosphidation. The CoP catalyst in this report exhibits a Tafel slope of 30.1mV/dec in 0.5M H2SO4 and 42.6mV/dec in 1M KOH. The high HER performance of our CoP catalysts is attributed to the rugae-like morphology which results in a high double-layer capacitance and high density of active sites, estimated as 7.77×1017sites/cm2. © 2015 Elsevier Ltd.

  16. Hydrogen economy

    Energy Technology Data Exchange (ETDEWEB)

    Pahwa, P.K.; Pahwa, Gulshan Kumar

    2013-10-01

    In the future, our energy systems will need to be renewable and sustainable, efficient and cost-effective, convenient and safe. Hydrogen has been proposed as the perfect fuel for this future energy system. The availability of a reliable and cost-effective supply, safe and efficient storage, and convenient end use of hydrogen will be essential for a transition to a hydrogen economy. Research is being conducted throughout the world for the development of safe, cost-effective hydrogen production, storage, and end-use technologies that support and foster this transition. This book discusses hydrogen economy vis-a-vis sustainable development. It examines the link between development and energy, prospects of sustainable development, significance of hydrogen energy economy, and provides an authoritative and up-to-date scientific account of hydrogen generation, storage, transportation, and safety.

  17. Synthesis of Cr2O3/TNTs nanocomposite and its photocatalytic hydrogen generation under visible light irradiation

    International Nuclear Information System (INIS)

    A novel Cr2O3/TNTs nanocomposite was prepared by loaded suitable amount of amorphous Cr2O3 on titanate nanotubes (TNTs) via hydrothermal reaction and impregnation process. XRD, SEM and TEM results demonstrated that the amorphous Cr2O3 nanoparticles were homogeneously dispersed on the surface of TNTs. The diffuse reflectance UV-visible absorption spectra exhibited that the spectral response of TNTs was extended to visible light region by coupled with Cr2O3. The 2.5Cr2O3/TNTs nanocomposite showed the highest activity of hydrogen generation by photocatalytic water-splitting under visible light irradiation (λ > 400 nm). The high activity of H2 evolution for Cr2O3/TNTs nanocomposites was associated with the donor level in the forbidden band of TNTs semiconductor provided by dopant Cr3+ and a probably photocatalytic mechanism was proposed.

  18. The hydrogen generation from alkaline NaBH4 solution by using electroplated amorphous Co–Ni–P film catalysts

    International Nuclear Information System (INIS)

    The amorphous Co–Ni–P films were electroplating on Cu sheets. The effects of NiSO4 concentrations on the deposit plating rate and the catalytic activities for NaBH4 hydrolysis were investigated. The surface morphology and phase structure of the deposited Co–Ni–P films were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The composition was analyzed by energy dispersive spectrometer (EDX). Experimental results showed that adding NiSO4 in Co–P bath could increase the deposition rate. When 0.01 M of NiSO4 was used, the highest deposition rate and the highest hydrogen generation rate of 3636 mL (min g-catalyst)−1 were obtained. The activation energy (Ea) for the NaBH4 hydrolysis was 38 kJ mol−1, which was comparable to the value of noble metal catalysts.

  19. Electrospun polyacrylonitrile nanofibers supported Ag/Pd nanoparticles for hydrogen generation from the hydrolysis of ammonia borane

    Science.gov (United States)

    Tong, Yan; Lu, Xiaofeng; Sun, Weining; Nie, Guangdi; Yang, Liu; Wang, Ce

    2014-09-01

    A high-performance hydrogen generation system based on the electrospun polyacrylonitrile (PAN)/Ag/Pd composite nanofibers, which were prepared by microwave reducing the electrospun PAN/AgNO3 nanofibers and followed by a replacement reaction has been demonstrated. The morphology of the as-prepared PAN/Ag/Pd composite nanofibers and the metal nanoparticles on the fibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. It has been demonstrated that the obtained PAN/Ag/Pd composite nanofibers possess fine morphology and high catalytic activities for H2 generation from aqueous solution of ammonia borane (NH3BH3, AB). The H2 generation test exhibited that the catalyst had excellent catalytic activity (with turnover frequency (TOF) of 377.2 mol H2 h-1 (mol Pd)-1), good recycle stability and easy-separation from the reaction system. This new kind of nanofibers possesses great potential application for the new clean energy development.

  20. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  1. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved ...

  2. Nitrogen and cobalt co-doped zinc oxide nanowires - Viable photoanodes for hydrogen generation via photoelectrochemical water splitting

    Science.gov (United States)

    Patel, Prasad Prakash; Hanumantha, Prashanth Jampani; Velikokhatnyi, Oleg I.; Datta, Moni Kanchan; Hong, Daeho; Gattu, Bharat; Poston, James A.; Manivannan, Ayyakkannu; Kumta, Prashant N.

    2015-12-01

    Photoelectrochemical (PEC) water splitting has been considered as a promising and environmentally benign approach for efficient and economic hydrogen generation by utilization of solar energy. Development of semiconductor materials with low band gap, high photoelectrochemical activity and stability has been of particular interest for a viable PEC water splitting system. In this study, Co doped ZnO, .i.e., (Zn0.95Co0.05)O nanowires (NWs) was selected as the composition for further co-doping with nitrogen by comparing solar to hydrogen efficiency (SHE) of ZnO NWs with that of various compositions of (Zn1-xCox)O NWs (x = 0, 0.05, 0.1). Furthermore, nanostructured vertically aligned Co and N-doped ZnO, .i.e., (Zn1-xCox)O:N NWs (x = 0.05) have been studied as photoanodes for PEC water splitting. An optimal SHE of 1.39% the highest reported so far to the best of our knowledge for ZnO based photoanodes was obtained for the co-doped NWs, (Zn0.95Co0.05)O:N - 600 NWs generated at 600 °C in ammonia atmosphere. Further, (Zn0.95Co0.05)O:N-600 NWs exhibited excellent photoelectrochemical stability under illumination compared to pure ZnO NWs. These promising results suggest the potential of (Zn0.95Co0.05)O:N-600 NWs as a viable photoanode in PEC water splitting cell. Additionally, theoretical first principles study conducted explains the beneficial effects of Co and N co-doping on both, the electronic structure and the band gap of ZnO.

  3. 钢铁厂制氢方法的比较及选用%Comparison and Selection of Hydrogen Generation Methods for Steel Plants

    Institute of Scientific and Technical Information of China (English)

    朱晓莉

    2014-01-01

    介绍了钢铁厂几种制氢方法的比较和选取,分析了各种制氢方法的特点和适用范围,提出工程设计中应考虑的一些因素来选择制氢方案,并提出最佳制氢方案。%Comparison and selection of several hydrogen generation methods for steel plants are introduced, the characteristics and applicable range of the hydrogen generation methods are analyzed, some factors influencing the selection to be considered in project design are presented and the best hydrogen generation plan is forwarded.

  4. Self-Sensitized Carbon Nitride Microspheres for Long-Lasting Visible-Light-Driven Hydrogen Generation.

    Science.gov (United States)

    Gu, Quan; Gao, Ziwei; Xue, Can

    2016-07-01

    A new type of metal-free photocatalyst is reported having a microsphere core of oxygen-containing carbon nitride and self-sensitized surfaces by covalently linked polymeric triazine dyes. These self-sensitized carbon nitride microspheres exhibit high visible-light activities in photocatalytic H2 generation with excellent stability for more than 100 h reaction. Comparing to the traditional g-C3 N4 with activities terminated at 450 nm, the polymeric triazine dyes on the carbon nitride microsphere surface allow for effective wide-range visible-light harvesting and extend the H2 generation activities up to 600 nm. It is believed that this new type of highly stable self-sensitized metal-free structure opens a new direction of future development of low-cost photocatalysts for efficient and long-term solar fuels production.

  5. Self-Sensitized Carbon Nitride Microspheres for Long-Lasting Visible-Light-Driven Hydrogen Generation.

    Science.gov (United States)

    Gu, Quan; Gao, Ziwei; Xue, Can

    2016-07-01

    A new type of metal-free photocatalyst is reported having a microsphere core of oxygen-containing carbon nitride and self-sensitized surfaces by covalently linked polymeric triazine dyes. These self-sensitized carbon nitride microspheres exhibit high visible-light activities in photocatalytic H2 generation with excellent stability for more than 100 h reaction. Comparing to the traditional g-C3 N4 with activities terminated at 450 nm, the polymeric triazine dyes on the carbon nitride microsphere surface allow for effective wide-range visible-light harvesting and extend the H2 generation activities up to 600 nm. It is believed that this new type of highly stable self-sensitized metal-free structure opens a new direction of future development of low-cost photocatalysts for efficient and long-term solar fuels production. PMID:27225827

  6. Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

    Science.gov (United States)

    McCollom, Thomas M.; Donaldson, Christopher

    2016-06-01

    Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

  7. Auxin-induced hydrogen sulfide generation is involved in lateral root formation in tomato.

    Science.gov (United States)

    Fang, Tao; Cao, Zeyu; Li, Jiale; Shen, Wenbiao; Huang, Liqin

    2014-03-01

    Similar to auxin, hydrogen sulfide (H2S), mainly produced by l-cysteine desulfhydrase (DES; EC 4.4.1.1) in plants, could induce lateral root formation. The objective of this study was to test whether H2S is also involved in auxin-induced lateral root development in tomato (Solanum lycopersicum L.) seedlings. We observed that auxin depletion-induced down-regulation of transcripts of SlDES1, decreased DES activity and endogenous H2S contents, and the inhibition of lateral root formation were rescued by sodium hydrosulfide (NaHS, an H2S donor). However, No additive effects were observed when naphthalene acetic acid (NAA) was co-treated with NaHS (lower than 10 mM) in the induction of lateral root formation. Subsequent work revealed that a treatment with NAA or NaHS could simultaneously induce transcripts of SlDES1, DES activity and endogenous H2S contents, and thereafter the stimulation of lateral root formation. It was further confirmed that H2S or HS(-), not the other sulfur-containing components derived from NaHS, was attributed to the stimulative action. The inhibition of lateral root formation and decreased of H2S metabolism caused by an H2S scavenger hypotaurine (HT) were reversed by NaHS, but not NAA. Molecular evidence revealed that both NaHS- or NAA-induced modulation of some cell cycle regulatory genes, including the up-regulation of SlCDKA;1, SlCYCA2;1, together with simultaneous down-regulation of SlKRP2, were differentially reversed by HT pretreatment. To summarize, above results clearly suggested that H2S might, at least partially, act as a downstream component of auxin signaling to trigger lateral root formation.

  8. Hydrogen peroxide generation by higher plant mitochondria oxidizing complex I or complex II substrates.

    Science.gov (United States)

    Braidot, E; Petrussa, E; Vianello, A; Macri, F

    1999-05-28

    The generation of H2O2 by isolated pea stem mitochondria, oxidizing either malate plus glutamate or succinate, was examined. The level of H2O2 was almost one order of magnitude higher when mitochondria were energized by succinate. The succinate-dependent H2O2 formation was abolished by malonate, but unaffected by rotenone. The lack of effect of the latter suggests that pea mitochondria were working with a proton motive force below the threshold value required for reverse electron transfer. The activation by pyruvate of the alternative oxidase was reflected in an inhibition of H2O2 formation. This effect was stronger when pea mitochondria oxidized malate plus glutamate. Succinate-dependent H2O2 formation was ca. four times lower in Arum sp. mitochondria (known to have a high alternative oxidase) than in pea mitochondria. An uncoupler (FCCP) completely prevented succinate-dependent H2O2 generation, while it only partially (40-50%) inhibited that linked to malate plus glutamate. ADP plus inorganic phosphate (transition from state 4 to state 3) also inhibited the succinate-dependent H2O2 formation. Conversely, that dependent on malate plus glutamate oxidation was unaffected by low and stimulated by high concentrations of ADP. These results show that the main bulk of H2O2 is formed during substrate oxidation at the level of complex II and that this generation may be prevented by either dissipation of the electrochemical proton gradient (uncoupling and transition state 4-state 3), or preventing its formation (alternative oxidase). Conversely, H2O2 production, dependent on oxidation of complex I substrate, is mainly lowered by the activation of the alternative oxidase. PMID:10371218

  9. Controllable hydrogen generation performance from Al/NaBH4 composite activated by La metal and CoCl2 salt in pure water

    Institute of Scientific and Technical Information of China (English)

    LIU Jianbo; FEI Yong; PAN Hua; FAN Meiqiang; WANG Liangliang; YAO Jun

    2012-01-01

    A novel composition of Al/NaBH4 mixture activated by La and CoCl2 in water for hydrogen generation was investigated.The composition had good stability at 298 K with high La content and low CoCl2 content,but presented good hydrogen generation performance with increasing global temperature.For example,The Al-15 wt.%La-5 wr.%CoCl2/NaBH4 mixture (mass ratio of 1∶1)yielded 1664 ml hydrogen/1 g mixture with 100% efficiency within 60 min at 333 K.The hydrogen generation rate and amount could be regulated by changing composition design,hydrolytic condition,etc.There existed a synergistic effect of La and CoCl2.Increasing La content was helpful to decrease crystal size of the mixture,but its hydrolysis byproduct La(OH)3 deposited on Al surface and had side effect on Al hydrolysis.Increased CoCl2 content was attributed to the producing of more actively catalytic sites Co2B/Al(OH)3 formed in the hydrolytic process.Co2B had dual catalytic effect on Al/NaBH4 hydrolysis.It deposited on Al surface and acted as a cathode of a micro galvanic cell.Co2B/Al(OH)3 was also a good promoter to NaBH4 hydrolysis.Therefore,the Al/NaBH4 mixture activated by La and CoCl2 may be applied as hydrogen generation material and the experimental data lays a foundation for designing practical hydrogen generators.

  10. New generation of full composite vessels for 70 MPa gaseous hydrogen storage : results and achievements of the French HyBou project

    Energy Technology Data Exchange (ETDEWEB)

    Nony, F. [CEA Materials, Monts (France); Weber, M. [Air Liquide, Paris (France); Tcharkhtchi, A. [Ecole Nationale Superieure d' Arts et Metiers, Paris (France); Lafarie-Frenot, M.C. [Ecole Nationale Superique De Mecanique et d' Aerotechnique, Poitiers (France); Perrier, O. [Raigi, Arbouville (France)

    2009-07-01

    The French collaborative Project known as HyBou explores hydrogen storage as a key enabling technology for the extensive use of hydrogen as an energy carrier. HyBou aims to develop robust, safe and efficient compressed gaseous hydrogen (CGH2) storage systems and validate innovative materials and processes suitable for storage vessel manufacturing with improved performance at low cost. The development of a new generation of type-4 70 MPa vessel was described along with a newly developed liner based on polyurethane materials. The new liner presents increased thermal stability, hydrogen barrier properties and cost effectiveness. The project also aims to evaluate the potential of new high resistance fibers and develop an improved thermosetting resin for composite winding with enhanced mechanical resistance and durability. A specific apparatus was therefore designed to characterize and evaluate coupled thermal and mechanical fatigue resistance in representative conditions.

  11. Hydrogen generation by aluminum corrosion in seawater promoted by suspensions of aluminum hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Soler, Lluis; Candela, Angelica Maria; Macanas, Jorge; Munoz, Maria; Casado, Juan [Centre Grup de Tecniques de Separacio en Quimica (GTS), Unitat de Quimica Analitica, Departament de Quimica, Universitat Autonoma de Barcelona, Edifici C - Campus de la UAB s/n, 08193 Bellaterra, Barcelona, Catalonia (Spain)

    2009-10-15

    Nowadays, new processes of H{sub 2} generation from water via Al corrosion are mainly limited by Al passivation. Here we report on the systematic assessment of H{sub 2} production by corrosion of Al in seawater suspensions prepared with NaAlO{sub 2}. The reported results are encouraging, since it was observed that seawater suspensions tested can prevent Al passivation during H{sub 2} evolution, reaching 100% yields at ca. 700 cm{sup 3} H{sub 2} min{sup -1}. XRD analysis revealed the formation of solid Al(OH){sub 3} (bayerite) in initial seawater suspensions. So, model suspensions were prepared using NaAlO{sub 2} + Al(OH){sub 3} in distilled water, which even improved the results obtained in seawater. Suspended particles of Al(OH){sub 3} act as nuclei in a mechanism of seeded crystallization, which prevents Al surface passivation. Moreover, a synergistic effect of Al(OH){sub 3} suspensions in combination with NaAlO{sub 2} solutions was key in promoting Al corrosion. The effect of NaCl in aqueous suspensions was also studied, but it was insignificant compared to this synergistic effect. The composition of suspensions was optimized and a 0.01 M NaAlO{sub 2} solution with 20 g dm{sup -3} Al(OH){sub 3} was selected as candidate to generate H{sub 2} at pH ca. 12 with high efficiency. Consecutive runs of the selected composition were performed obtaining ca. 90% yields in all of them. (author)

  12. A LOPA application to the hydrogen cooling system of the main electric generator of a nuclear power plant

    Energy Technology Data Exchange (ETDEWEB)

    Vasconcelos, Flavia M.; Frutuoso e Melo, Paulo Fernando Ferreira [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil)]. E-mails: flaviamvasconcelos@gmail.com; frutuoso@con.ufrj.br; Saldanha, P.L. [Comissao Nacional de Energia Nuclear (CNEN), Rio de Janeiro, RJ (Brazil). Coordenacao de Reatores]. E-mail: saldanha@cnen.gov.br

    2008-07-01

    The Layer of Protection Analysis (LOPA) is a powerful analytical tool for assessing the adequacy of protection layers used to mitigate risks in a process plant. LOPA applies semi-quantitative measures to evaluate the frequency of potential incidents and the probability of failure of protection layers. This paper presents an application of the Layer of Protection Analysis technique to a nuclear power plant in order to evaluate the cooling system of an electric generator, so as to identify scenarios that might lead to a plant shutdown. Next, the frequencies of occurrence of these events and the probability of failure on demand of the independent protection layers are determined. Here a difficulty is related to the lack of failure and initiating event data. The consequences identified are listed as impact events and are classified as to their severity level. The initiating causes are listed for each impact event and the likelihood is estimated for each initiating cause. Independent Protection Layers (ILPs) are listed. The mitigated event likelihood is studied and additional ILPs can be evaluated and added to reduce the risk. As a conclusion, LOPA demonstrated that the hydrogen inner-cooling electric generator system is in compliance with the risk scenarios adopted for this study. Some suggestions were made in order to automate some manual actions to increase the system reliability. (author)

  13. The Effect of Herbicides on Hydrogen Peroxide Generation in Isolated Vacuoles of Red Beet Root (Beta vulgaris L.

    Directory of Open Access Journals (Sweden)

    E.V. Pradedova

    2015-12-01

    Full Text Available Influence of herbicides on the hydrogen peroxide generation in vacuolar extracts of red beet root (Beta vulgaris L. was investigated. Belonging to different chemical classes of herbicide compounds have been used. Herbicides differ from each other in the mechanism of effects on plants. Clopyralid (aromatic acid herbicide, derivative of picolinic acid and 2.4-D (phenoxyacetic herbicide, characterized by hormone-like effects, contributed to the formation of H2O2 in vacuolar extracts. Fluorodifen (nitrophenyl ether herbicide and diuron (urea herbicide also have increased contents H2O2. These compounds inhibit the electron transport, photosynthesis, and photorespiration in sensitive plants. Herbicidal effect of glyphosate (organophosphorus herbicide is due to the inhibition of amino acid synthesis in plant cells. Glyphosate did not affect the content of H2O2 in vacuolar extracts. Herbicide dependent H2O2-generation did not occur with oxidoreductase inhibitors, potassium cyanide and sodium azide. The results suggest that the formation of ROS in the vacuoles due to activity of oxidoreductases, which could interact with herbicides.

  14. Generation of hydrogen from polyvinyl chloride by milling and heating with CaO and Ni(OH)2.

    Science.gov (United States)

    Tongamp, William; Zhang, Qiwu; Shoko, Miyagi; Saito, Fumio

    2009-08-15

    This work discusses an alternative process option for the treatment of polyvinyl chloride (PVC) by producing hydrogen (H(2)) gas, at the same time fixing chlorine for proper environmental control. In the first-stage, a milling operation is performed in a planetary ball mill to obtain a mixture of PVC sample with CaO and Ni(OH)(2) to be used as feed in the second-step, involving heating of the milled product. Analyses by thermogravimetry-mass spectroscopy (TG-MS) and gas chromatography (GC) showed H(2), CH(4), CO and CO(2) as main constituents. The results clearly show that addition of Ni(OH)(2) to provide nickel as catalyst and CaO as adsorbent to fix CO(2) and HCl gases generated during heating, assisted in clean H(2) generation with concentration near 90% at temperatures between 450 and 550 degrees C. Analyses of solids after heating by X-ray diffraction and TG-DTA techniques showed both CaOHCl and CaCO(3) as main phases in the product. This process could be developed to treat PVC wastes together with other polymers and/or plastic wastes for production of H(2) gas.

  15. Involvement of Hydrogen Peroxide Generated by Polyamine Oxidative Degradation in the Development of Lateral Roots in Soybean

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In order to determine whether hydrogen peroxide (H2O2) generated by polyamine oxidative degradation is involved in the development of lateral roots in soybean, the length and the number of lateral roots, the activities of polyamine oxidases and diamine oxidases, and the endogenous free polyamine and H2O2 content were analyzed in soybean (Glycine max (Linn.) Merr.) main roots of 2-d-old seedlings after treatments for 2 d with exogenous β-hydroxyethylhydrazine (an inhibitor of polyamine oxidases), H2O2, putrescine, cyclohexylamine (an inhibitor of spermidine synthase) or N,N'-dimethylthiourea (a scavenger of hydrogen peroxide).β-hydroxyethylhydrazine treatment strongly inhibited the development of lateral roots in soybean seedlings,reduced the activities of polyamine oxidases and diamine oxidases, decreased H2O2 levels, and led to the accumulation of endogenous polyamines in the main roots. The inhibitory effect of β-hydroxyethylhydrazine on root development could be alleviated by exogenously applied 10 μmol/L H2O2 (a major product of polyamine oxidation). Treatment with cyclohexylamine and putrescine promoted root growth slightly, but treatment with cyclohexylamine plus N,N'-dimethylthiourea or putrescine plus N,N'-dimethylthiourea prevented the development of soybean lateral roots. The effects of these treatments on the development of soybean lateral roots were consistent with the changes in endogenous H2O2 levels. These results suggest that the development of soybean lateral roots is associated with the oxidative degradation of polyamines, and that their products,especially H2O2, are likely to play an important role in the growth of soybean lateral roots.

  16. Saturation Ion Current Densities in Inductively Coupled Hydrogen Plasma Produced by Large-Power Radio Frequency Generator

    Science.gov (United States)

    Wang, Songbai; Lei, Guangjiu; Bi, Zhenhua; Ghomi, H.; Yang, Size; Liu, Dongping

    2016-09-01

    An experimental investigation of the saturation ion current densities (Jions) in hydrogen inductively coupled plasma (ICP) produced by a large-power (2-32 kW) radio frequency (RF) generator is reported, then some reasonable explanations are given out. With the increase of RF power, the experimental results show three stages: in the first stage (2-14 kW), the electron temperature will rise with the increase of RF power in the ICP, thus, the Jions increases continually as the electron temperature rises in the ICP. In the second stage (14-20 kW), as some H- ions lead to the mutual neutralization (MN), the slope of Jions variation firstly decreases then increases. In the third stage (20-32 kW), both the electronic detachment (ED) and the associative detachment (AD) in the ICP result in the destruction of H- ions, therefore, the increased amplitude of the Jions in the third stage is weaker than the one in the first stage. In addition, with the equivalent transformer model, we successfully explain that the Jions at different radial locations in ICP has the same rule. Finally, it is found that the Jions has nothing to do with the outer/inner puffing gas pressure ratio, which is attributed to the high-speed movement of hydrogen molecules. supported by the National Magnetic Confinement Fusion Science Program of China (Nos. 2011GB108011 and 2010GB103001), the Major International (Regional) Project Cooperation and Exchanges of China (No. 11320101005) and the Startup Fund from Fuzhou University (No. 510071)

  17. Enhanced Hydrogen Generation Properties of MgH2-Based Hydrides by Breaking the Magnesium Hydroxide Passivation Layer

    Directory of Open Access Journals (Sweden)

    Liuzhang Ouyang

    2015-05-01

    Full Text Available Due to its relatively low cost, high hydrogen yield, and environmentally friendly hydrolysis byproducts, magnesium hydride (MgH2 appears to be an attractive candidate for hydrogen generation. However, the hydrolysis reaction of MgH2 is rapidly inhibited by the formation of a magnesium hydroxide passivation layer. To improve the hydrolysis properties of MgH2-based hydrides we investigated three different approaches: ball milling, synthesis of MgH2-based composites, and tuning of the solution composition. We demonstrate that the formation of a composite system, such as the MgH2/LaH3 composite, through ball milling and in situ synthesis, can improve the hydrolysis properties of MgH2 in pure water. Furthermore, the addition of Ni to the MgH2/LaH3 composite resulted in the synthesis of LaH3/MgH2/Ni composites. The LaH3/MgH2/Ni composites exhibited a higher hydrolysis rate—120 mL/(g·min of H2 in the first 5 min—than the MgH2/LaH3 composite— 95 mL/(g·min—without the formation of the magnesium hydroxide passivation layer. Moreover, the yield rate was controlled by manipulation of the particle size via ball milling. The hydrolysis of MgH2 was also improved by optimizing the solution. The MgH2 produced 1711.2 mL/g of H2 in 10 min at 298 K in the 27.1% ammonium chloride solution, and the hydrolytic conversion rate reached the value of 99.5%.

  18. Polyhydride complexes for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, C.M. [Univ. of Hawaii, Honolulu, HI (United States)

    1995-09-01

    Polyhydride metal complexes are being developed for application in hydrogen storage. Efforts have focused on developing complexes with improved available hydrogen weight percentages. We have explored the possibility that complexes containing aromatic hydrocarbon ligands could store hydrogen at both the metal center and in the ligands. We have synthesized novel indenyl hydride complexes and explored their reactivity with hydrogen. The reversible hydrogenation of [IrH{sub 3}(PPh{sub 3})({eta}{sup 5}-C{sub 10}H{sub 7})]{sup +} has been achieved. While attempting to prepare {eta}{sup 6}-tetrahydronaphthalene complexes, we discovered that certain polyhydride complexes catalyze both the hydrogenation and dehydrogenation of tetrahydronaphthalene.

  19. Heat Balance Study on Integrated Cycles for Hydrogen and Electricity Generation in VHTR

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Il; Yoo, Yeon Jae [Hyundai Engineering Company Ltd., Seoul (Korea, Republic of); Heo, Gyunyoung; Park, Soyoung; Kang, Yeon Kwan [Kyung Hee University, Yongin (Korea, Republic of)

    2015-05-15

    A gas cooled reactor has the advantage of being able to create a higher temperature coolant than a water cooled reactor. We can take advantage of supplying electricity as well as process heat. Recently, taking the export opportunity of a commercial nuclear power plants in UAE, Middle East area where politically stable and resource-rich seems promising for further nuclear business. Even if construction cost is more expensive than water cooled reactors, a high temperature gas cooled reactor is an attractive option from the viewpoint of safety. It can reduce the domestic use of fossil fuels and secure power and water, which is the most important part of people's daily life. All- Electrical Mode (AEM) operates only for the purpose of electricity generation. Rated Cogeneration Mode (RCM) uses approximately 60% of the total flow as process heat. We use a part flow exiting the high pressure turbine of end portion to the process heat, and the flow channel to a heat exchanger and a deaerator is changed at this time. Turbine Bypass Mode (TBM) will be used to supply the process heat by blocking all flow to the turbines.

  20. Heat Balance Study on Integrated Cycles for Hydrogen and Electricity Generation in VHTR

    International Nuclear Information System (INIS)

    A gas cooled reactor has the advantage of being able to create a higher temperature coolant than a water cooled reactor. We can take advantage of supplying electricity as well as process heat. Recently, taking the export opportunity of a commercial nuclear power plants in UAE, Middle East area where politically stable and resource-rich seems promising for further nuclear business. Even if construction cost is more expensive than water cooled reactors, a high temperature gas cooled reactor is an attractive option from the viewpoint of safety. It can reduce the domestic use of fossil fuels and secure power and water, which is the most important part of people's daily life. All- Electrical Mode (AEM) operates only for the purpose of electricity generation. Rated Cogeneration Mode (RCM) uses approximately 60% of the total flow as process heat. We use a part flow exiting the high pressure turbine of end portion to the process heat, and the flow channel to a heat exchanger and a deaerator is changed at this time. Turbine Bypass Mode (TBM) will be used to supply the process heat by blocking all flow to the turbines

  1. Electrochemical scaffold generates localized, low concentration of hydrogen peroxide that inhibits bacterial pathogens and biofilms

    Science.gov (United States)

    Sultana, Sujala T.; Atci, Erhan; Babauta, Jerome T.; Mohamed Falghoush, Azeza; Snekvik, Kevin R.; Call, Douglas R.; Beyenal, Haluk

    2015-01-01

    We hypothesized that low concentrations of H2O2 could be generated through the electrochemical conversion of oxygen by applying an electric potential to a conductive scaffold and produce a low, but constant, concentration of H2O2 that would be sufficient to destroy biofilms. To test our hypothesis we used a multidrug-resistant Acinetobacter baumannii strain, because this species is often implicated in difficult-to-treat biofilm infections. We used conductive carbon fabric as the scaffold material (“e-scaffold”). In vitro experiments demonstrated the production of a maximum constant concentration of ~25 μM H2O2 near the e-scaffold surface. An e-scaffold was overlaid onto an existing A. baumannii biofilm, and within 24 h there was a ~4-log reduction in viable bacteria with an ~80% decrease in biofilm surface coverage. A similar procedure was used to overlay an e-scaffold onto an existing A. baumannii biofilm that was grown on a porcine explant. After 24 h, there was a ~3-log reduction in viable bacteria from the infected porcine explants with no observable damage to the underlying mammalian tissue based on a viability assay and histology. This research establishes a novel foundation for an alternative antibiotic-free wound dressing to eliminate biofilms. PMID:26464174

  2. Photoelectrochemical water splitting and hydrogen generation by a spontaneously formed InGaN nanowall network

    Energy Technology Data Exchange (ETDEWEB)

    Alvi, N. H., E-mail: nhalvi@isom.upm.es, E-mail: r.noetzel@isom.upm.es; Soto Rodriguez, P. E. D.; Kumar, Praveen; Gómez, V. J.; Aseev, P.; Nötzel, R., E-mail: nhalvi@isom.upm.es, E-mail: r.noetzel@isom.upm.es [ISOM Institute for Systems Based on Optoelectronics and Microtechnology, ETSI Telecomunicación, Universidad Politécnica de Madrid, Ciudad Universitaria s/n, 28040 Madrid (Spain); Alvi, A. H. [Department of Physics, Government College University, Faisalabad (Pakistan); Alvi, M. A. [Department of Chemistry, Government College University, Faisalabad (Pakistan); Willander, M. [Department of Science and Technology (ITN), Campus Norrköping, Linköping University, 60174 Norrköping (Sweden)

    2014-06-02

    We investigate photoelectrochemical water splitting by a spontaneously formed In-rich InGaN nanowall network, combining the material of choice with the advantages of surface texturing for light harvesting by light scattering. The current density for the InGaN-nanowalls-photoelectrode at zero voltage versus the Ag/AgCl reference electrode is 3.4 mA cm{sup −2} with an incident-photon-to-current-conversion efficiency (IPCE) of 16% under 350 nm laser illumination with 0.075 W·cm{sup −2} power density. In comparison, the current density for a planar InGaN-layer-photoelectrode is 2 mA cm{sup −2} with IPCE of 9% at zero voltage versus the Ag/AgCl reference electrode. The H{sub 2} generation rates at zero externally applied voltage versus the Pt counter electrode per illuminated area are 2.8 and 1.61 μmol·h{sup −1}·cm{sup −2} for the InGaN nanowalls and InGaN layer, respectively, revealing ∼57% enhancement for the nanowalls.

  3. Hydrogen generation by metal corrosion in simulated Waste Isolation Pilot Plant environments

    International Nuclear Information System (INIS)

    The corrosion and gas-generation characteristics of three material types: low-carbon steel (the current waste packaging material for the Waste Isolation Pilot Plant), Cu-base materials, and Ti-base materials were determined in both the liquid and vapor phase of Brine A, a brine representative of an intergranular Salado Formation brine. Test environments included anoxic brine and anoxic brine with overpressures of CO2, H2S, and H2. Low-carbon steel reacted at a slow, measurable rate with anoxic brine, liberating H2 on an equimolar basis with Fe reacted. Presence of CO2 caused the initial reaction to proceed more rapidly, but CO2-induced passivation stopped the reaction if the CO2 were present in sufficient quantities. Low-carbon steel immersed in brine with H2S showed no reaction, apparently because of passivation of the steel by formation of a protective iron sulfide reaction product. Cu- and Ti-base materials showed essentially no corrosion when exposed to brine and overpressures of N2, CO2, and H2S except for the rapid and complete reaction between Cu-base materials and H2S. No significant reaction took place on any material in any environment in the vapor-phase exposures

  4. A comparison of hydroxyl radical and hydrogen peroxide generation in ambient particle extracts and laboratory metal solutions

    Science.gov (United States)

    Shen, Huiyun; Anastasio, Cort

    2012-01-01

    Generation of reactive oxygen species (ROS) - including superoxide ( rad O 2-), hydrogen peroxide (HOOH), and hydroxyl radical ( rad OH) - has been suggested as one mechanism underlying the adverse health effects caused by ambient particulate matter (PM). In this study we compare HOOH and rad OH production from fine and coarse PM collected at an urban (Fresno) and rural (Westside) site in the San Joaquin Valley (SJV) of California, as well as from laboratory solutions containing dissolved copper or iron. Samples were extracted in a cell-free, phosphate-buffered saline (PBS) solution containing 50 μM ascorbate (Asc). In our laboratory solutions we find that Cu is a potent source of both HOOH and rad OH, with approximately 90% of the electrons that can be donated from Asc ending up in HOOH and rad OH after 4 h. In contrast, in Fe solutions there is no measurable HOOH and only a modest production of rad OH. Soluble Cu in the SJV PM samples is also a dominant source of HOOH and rad OH. In both laboratory copper solutions and extracts of ambient particles we find much more production of HOOH compared to rad OH: e.g., HOOH generation is approximately 30-60 times faster than rad OH generation. The formation of HOOH and rad OH are positively correlated, with roughly 3% and 8% of HOOH converted to rad OH after 4 and 24 h of extraction, respectively. Although the SJV PM produce much more HOOH than rad OH, since rad OH is a much stronger oxidant it is unclear which species might be more important for oxidant-mediated toxicity from PM inhalation.

  5. Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN(3) -Pincer Ligand.

    Science.gov (United States)

    Pan, Yupeng; Pan, Cheng-Ling; Zhang, Yufan; Li, Huaifeng; Min, Shixiong; Guo, Xunmun; Zheng, Bin; Chen, Hailong; Anders, Addison; Lai, Zhiping; Zheng, Junrong; Huang, Kuo-Wei

    2016-05-01

    An unsymmetrically protonated PN(3) -pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved.

  6. Hydrogen generation by metal corrosion in simulated Waste Isolation Pilot Plant environments. Final report

    International Nuclear Information System (INIS)

    The corrosion and gas-generation characteristics of four material types: low-carbon steel (the current waste packaging material for the Waste Isolation Pilot Plant), Cu-base and Ti-base (alternative packaging) materials, and Al-base (simulated waste) materials were determined in both the liquid and vapor phase of Brine A, a brine representative of an intergranular Salado Formation brine. Test environments consisted primarily of anoxic brine with overpressures of N2, CO2, H2S, and H2. Limited tests of low-carbon steel were also performed in simulated-backfill environments and in brine environments with pH values ranging from 3 to 11. Low-carbon steel reacted at a slow, measurable rate with anoxic brine, liberating H2 on an equimolar basis with Fe reacted. Presence of CO2 caused the initial reaction to proceed more rapidly, but CO2-induced passivation stopped the reaction if the CO2 were present in sufficient quantities. Addition of H2S to a CO2-passivated system caused reversal of the passivation. Low-carbon steel immersed in brine with H2S showed no reaction, apparently because of passivation of the steel by formation of FeS. Addition of CO2 to an H2S-passivated system did not reverse the passivation. Cu- and Ti-base materials showed essentially no corrosion when exposed to brine and overpressures of N2, CO2, and H2S except for the rapid and complete reaction between Cu-base materials and H2S. The Al-base materials reacted at approximately the same rate as low-carbon steel when immersed in anoxic Brine A; considerably more rapidly in the presence of CO2 or H2S; and much more rapidly when iron was present in the system as a brine contaminant. High-purity Al was much more susceptible to corrosion than the 6061 alloy. No significant reaction took place on any material in any environment in the vapor-phase exposures

  7. Hydrogenation of the alpha,beta-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and Prenal over Pt Single Crystals: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Kliewer, C.J.; Somorjai, G.A.

    2008-11-26

    Sum-frequency generation vibrational spectroscopy (SFG-VS) and kinetic measurements using gas chromatography have been used to study the surface reaction intermediates during the hydrogenation of three {alpha},{beta}-unsaturated aldehydes, acrolein, crotonaldehyde, and prenal, over Pt(111) at Torr pressures (1 Torr aldehyde, 100 Torr hydrogen) in the temperature range of 295K to 415K. SFG-VS data showed that acrolein has mixed adsorption species of {eta}{sub 2}-di-{sigma}(CC)-trans, {eta}{sub 2}-di-{sigma}(CC)-cis as well as highly coordinated {eta}{sub 3} or {eta}{sub 4} species. Crotonaldehyde adsorbed to Pt(111) as {eta}{sub 2} surface intermediates. SFG-VS during prenal hydrogenation also suggested the presence of the {eta}{sub 2} adsorption species, and became more highly coordinated as the temperature was raised to 415K, in agreement with its enhanced C=O hydrogenation. The effect of catalyst surface structure was clarified by carrying out the hydrogenation of crotonaldehyde over both Pt(111) and Pt(100) single crystals while acquiring the SFG-VS spectra in situ. Both the kinetics and SFG-VS showed little structure sensitivity. Pt(100) generated more decarbonylation 'cracking' product while Pt(111) had a higher selectivity for the formation of the desired unsaturated alcohol, crotylalcohol.

  8. Iridium-Catalyzed Selective Isomerization of Primary Allylic Alcohols.

    Science.gov (United States)

    Li, Houhua; Mazet, Clément

    2016-06-21

    This Account presents the development of the iridium-catalyzed isomerization of primary allylic alcohols in our laboratory over the past 8 years. Our initial interest was driven by the long-standing challenge associated with the development of a general catalyst even for the nonasymmetric version of this seemingly simple chemical transformation. The added value of the aldehyde products and the possibility to rapidly generate molecular complexity from readily accessible allylic alcohols upon a redox-economical isomerization reaction were additional sources of motivation. Certainly influenced by the success story of the related isomerization of allylic amines, most catalysts developed for the selective isomerization of allylic alcohols were focused on rhodium as a transition metal of choice. Our approach has been based on the commonly accepted precept that hydrogenation and isomerization are often competing processes, with the latter being usually suppressed in favor of the former. The cationic iridium complexes [(Cy3P)(pyridine)Ir(cod)]X developed by Crabtree (X = PF6) and Pfaltz (X = BArF) are usually considered as the most versatile catalysts for the hydrogenation of allylic alcohols. Using molecular hydrogen to generate controlled amounts of the active form of these complexes but performing the reaction in the absence of molecular hydrogen enabled deviation from the typical hydrogenation manifold and favored exclusively the isomerization of allylic alcohols into aldehydes. Isotopic labeling and crossover experiments revealed the intermolecular nature of the process. Systematic variation of the ligand on the iridium center allowed us to identify the structural features beneficial for catalytic activity. Subsequently, three generations of chiral catalysts have been investigated and enabled us to reach excellent levels of enantioselectivity for a wide range of 3,3-disubstituted aryl/alkyl and alkyl/alkyl primary allylic alcohols leading to β-chiral aldehydes. The

  9. Novel strategies for asymmetric hydrogenation reactions

    OpenAIRE

    Chen, Dianjun

    2011-01-01

    This thesis describes two novel possibilities for asymmetric hydrogenation: enantioselective hydrogenation using chiral ionic liquid systems and metal-free hydrogenation with boranes. In the first part, asymmetric hydrogenation systems using chiral ionic liquids in combination with racemic rhodium catalyst are presented. Enantioselectivities up to 69% ee were achieved in homogeneous Rh-catalyzed hydrogenation with tropos ligand (BIPHEP, sulfonated BIPHEP) in a proline derived cation chiral io...

  10. Site-Specific, Covalent Immobilization of Dehalogenase ST2570 Catalyzed by Formylglycine-Generating Enzymes and Its Application in Batch and Semi-Continuous Flow Reactors.

    Science.gov (United States)

    Jian, Hui; Wang, Yingwu; Bai, Yan; Li, Rong; Gao, Renjun

    2016-01-01

    Formylglycine-generating enzymes can selectively recognize and oxidize cysteine residues within the sulfatase sub motif at the terminus of proteins to form aldehyde-bearing formylglycine (FGly) residues, and are normally used in protein labeling. In this study, an aldehyde tag was introduced to proteins using formylglycine-generating enzymes encoded by a reconstructed set of the pET28a plasmid system for enzyme immobilization. The haloacid dehalogenase ST2570 from Sulfolobus tokodaii was used as a model enzyme. The C-terminal aldehyde-tagged ST2570 (ST2570CQ) exhibited significant enzymological properties, such as new free aldehyde groups, a high level of protein expression and improved enzyme activity. SBA-15 has widely been used as an immobilization support for its large surface and excellent thermal and chemical stability. It was functionalized with amino groups by aminopropyltriethoxysilane. The C-terminal aldehyde-tagged ST2570 was immobilized to SBA-15 by covalent binding. The site-specific immobilization of ST2570 avoided the chemical denaturation that occurs in general covalent immobilization and resulted in better fastening compared to physical adsorption. The site-specific immobilized ST2570 showed 3-fold higher thermal stability, 1.2-fold higher catalytic ability and improved operational stability than free ST2570. The site-specific immobilized ST2570 retained 60% of its original activity after seven cycles of batch operation, and it was superior to the ST2570 immobilized to SBA-15 by physical adsorption, which loses 40% of its original activity when used for the second time. It is remarkable that the site-specific immobilized ST2570 still retained 100% of its original activity after 10 cycles of reuse in the semi-continuous flow reactor. Overall, these results provide support for the industrial-scale production and application of site-specific, covalently immobilized ST2570. PMID:27409601

  11. Site-Specific, Covalent Immobilization of Dehalogenase ST2570 Catalyzed by Formylglycine-Generating Enzymes and Its Application in Batch and Semi-Continuous Flow Reactors

    Directory of Open Access Journals (Sweden)

    Hui Jian

    2016-07-01

    Full Text Available Formylglycine-generating enzymes can selectively recognize and oxidize cysteine residues within the sulfatase sub motif at the terminus of proteins to form aldehyde-bearing formylglycine (FGly residues, and are normally used in protein labeling. In this study, an aldehyde tag was introduced to proteins using formylglycine-generating enzymes encoded by a reconstructed set of the pET28a plasmid system for enzyme immobilization. The haloacid dehalogenase ST2570 from Sulfolobus tokodaii was used as a model enzyme. The C-terminal aldehyde-tagged ST2570 (ST2570CQ exhibited significant enzymological properties, such as new free aldehyde groups, a high level of protein expression and improved enzyme activity. SBA-15 has widely been used as an immobilization support for its large surface and excellent thermal and chemical stability. It was functionalized with amino groups by aminopropyltriethoxysilane. The C-terminal aldehyde-tagged ST2570 was immobilized to SBA-15 by covalent binding. The site-specific immobilization of ST2570 avoided the chemical denaturation that occurs in general covalent immobilization and resulted in better fastening compared to physical adsorption. The site-specific immobilized ST2570 showed 3-fold higher thermal stability, 1.2-fold higher catalytic ability and improved operational stability than free ST2570. The site-specific immobilized ST2570 retained 60% of its original activity after seven cycles of batch operation, and it was superior to the ST2570 immobilized to SBA-15 by physical adsorption, which loses 40% of its original activity when used for the second time. It is remarkable that the site-specific immobilized ST2570 still retained 100% of its original activity after 10 cycles of reuse in the semi-continuous flow reactor. Overall, these results provide support for the industrial-scale production and application of site-specific, covalently immobilized ST2570.

  12. Parameters critical to muon-catalyzed fusion

    International Nuclear Information System (INIS)

    We have demonstrated that muon catalysis cycling rates increase rapidly with increasing deuterium-tritium gas temperatures and densities. Furthermore, muon-capture losses are significantly smaller than predicted before the experiments. There remains a significant gap between observation and theoretical expectation for the muon-alpha sticking probability in dense d-t mixtures. We have been able to achieve muon-catalyzed yields of 150 fusion/muon (average). While the fusion energy thereby released significantly exceeds expectations, enhancements by nearly a factor of twenty would be needed to realize energy applications for a pure (non-hybrid) muon-catalyzed fusion reactor. The process could be useful in tritium-breeding schemes. We have also explored a new form of cold nuclear fusion which occurs when hydrogen isotopes are loaded into metals. 22 refs., 10 figs

  13. Ruthenium(0) nanoparticles supported on multiwalled carbon nanotube as highly active catalyst for hydrogen generation from ammonia-borane.

    Science.gov (United States)

    Akbayrak, Serdar; Ozkar, Saim

    2012-11-01

    Ruthenium(0) nanoparticles supported on multiwalled carbon nanotubes (Ru(0)@MWCNT) were in situ formed during the hydrolysis of ammonia-borane (AB) and could be isolated from the reaction solution by filtration and characterized by ICP-OES, XRD, TEM, SEM, EDX, and XPS techniques. The results reveal that ruthenium(0) nanoparticles of size in the range 1.4-3.0 nm are well-dispersed on multiwalled carbon nanotubes. They were found to be highly active catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value of 329 min⁻¹. The reusability experiments show that Ru(0)@MWCNTs are isolable and redispersible in aqueous solution; when redispersed they are still active catalyst in the hydrolysis of AB exhibiting a release of 3.0 equivalents of H₂ per mole of NH₃BH₃ and preserving 41% of the initial catalytic activity even after the fourth run of hydrolysis. The lifetime of Ru(0)@MWCNTs was measured as 26400 turnovers over 29 h in the hydrolysis of AB at 25.0 ± 0.1 °C before deactivation. The work reported here also includes the kinetic studies depending on the temperature to determine the activation energy of the reaction (E(a) = 33 ± 2 kJ/mol) and the effect of catalyst concentration on the rate of the catalytic hydrolysis of AB, respectively. PMID:23113804

  14. Hydrogen generation from catalytic hydrolysis of sodium borohydride solution using Cobalt-Copper-Boride (Co-Cu-B) catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Xin-Long; Yuan, Xianxia; Jia, Chao; Ma, Zi-Feng [Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China)

    2010-10-15

    Co-Cu-B, as a catalyst toward hydrolysis of sodium borohydride solution, has been prepared through chemical reduction of metal salts, CoCl{sub 2}.6H{sub 2}O and CuCl{sub 2}, by an alkaline solution composed of 7.5wt% NaBH{sub 4} and 7.5wt% NaOH. The effects of Co/Cu molar ratio, calcination temperature, NaOH and NaBH{sub 4} concentration and reaction temperature on catalytic activity of Co-Cu-B for hydrogen generation from alkaline NaBH{sub 4} solution have been studied. X-ray diffraction (XRD), scanning electron microscope (SEM) and Nitrogen adsorption-desorption isotherm have been employed to understand the results. The Co-Cu-B catalyst with a Co/Cu molar ratio of 3:1 and calcinated at 400 C showed the best catalytic activity at ambient temperature. The activation energy of this catalytic reaction is calculated to be 49.6 kJ mol{sup -1}. (author)

  15. Evaluating the generation efficiency of hydrogen peroxide in water by pulsed discharge over water surface and underwater bubbling pulsed discharge

    Science.gov (United States)

    Shang, Kefeng; Li, Jie; Wang, Xiaojing; Yao, Dan; Lu, Na; Jiang, Nan; Wu, Yan

    2016-01-01

    Pulsed electric discharge over water surface/in water has been used to generate reactive species for decomposing the organic compounds in water, and hydrogen peroxide (H2O2) is one of the strong reactive species which can be decomposed into another stronger oxidative species, hydroxyl radical. The production efficacy of H2O2 by a gas phase pulsed discharge over water surface and an underwater bubbling pulsed discharge was evaluated through diagnosis of H2O2 by a chemical probe method. The experimental results show that the yield and the production rate of H2O2 increased with the input energy regardless of the electric discharge patterns, and the underwater bubbling pulsed discharge was more advantageous for H2O2 production considering both the yield and the production rate of H2O2. Results also indicate that the electric discharge patterns also influenced the water solution properties including the conductivity, the pH value and the water temperature.

  16. Performance of Ni-based, Fe-based and Co-based Oxygen Carriers in Chemical-Looping Hydrogen Generation

    Institute of Scientific and Technical Information of China (English)

    Liang Hao; Zhang Xiwen; Fang Xiangchen; Yuan Honggang

    2013-01-01

    Ni-based, Fe-based and Co-based oxygen carriers with perovskite oxides used as the supports were prepared by citric acid complexation method. The oxygen carriers were characterized by thermal analysis, H2-temperature-programmed reduction and X-ray diffraction methods. Performance tests were evaluated through Chemical-Looping Hydrogen Genera-tion in a ifxed-bed reactor operating at atmospheric pressure. The characterization results showed that all samples were composed of metal oxides and perovskite oxides. Performance results indicated that CH4 conversion over the oxygen car-riers decreased in the following order:NiO/LaNiO3>Co2O3/LaCoO3>Fe2O3/LaFeO3. The ability of NiO/LaNiO3 and Fe2O3/LaFeO3 to decompose water was stronger than that of Co2O3/LaCoO3 as evidenced by our experiments. H2 amounting to 80 mL upon reacting on methane in every cycle could be completely oxidized by NiO/LaNiO3 at 900℃in the period from the third cycle to the eighth cycle.

  17. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

    2005-12-15

    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  18. Facile synthesis of polypyrrole functionalized nickel foam with catalytic activity comparable to Pt for the poly-generation of hydrogen and electricity

    Science.gov (United States)

    Tang, Tiantian; Li, Kan; Shen, Zhemin; Sun, Tonghua; Wang, Yalin; Jia, Jinping

    2016-01-01

    Polypyrrole functionalized nickel foam is facilely prepared through the potentiostatic electrodeposition. The PPy-functionalized Ni foam functions as a hydrogen-evolution cathode in a rotating disk photocatalytic fuel cell, in which hydrogen energy and electric power are generated by consuming organic wastes. The PPy-functionalized Ni foam cathode exhibits stable catalytic activities after thirteen continuous runs. Compared with net or plate structure, the Ni foam with a unique three-dimensional reticulate structure is conducive to the electrodeposition of PPy. Compared with Pt-group electrode, PPy-coated Ni foam shows a satisfactory catalytic performance for the H2 evolution. The combination of PPy and Ni forms a synergistic effect for the rapid trapping and removal of proton from solution and the catalytic reduction of proton to hydrogen. The PPy-functionalized Ni foam could be applied in photocatalytic and photoelectrochemical generation of H2. In all, we report a low cost, high efficient and earth abundant PPy-functionalized Ni foam with a satisfactory catalytic activities comparable to Pt for the practical application of poly-generation of hydrogen and electricity.

  19. 仿生构建具有一氧化氮自催化生成功能的人工血管材料%Layer-by-layer assembled selenium containing mimic artificial blood vessels with catalyzing NO generation

    Institute of Scientific and Technical Information of China (English)

    李岩冬; 王恺; 孔梅梅; 武文洁; 安军; 陈思原; 洪彦航; 孔德领; 王淑芳

    2011-01-01

    目的 利用有机硒催化一氧化氮(No)供体释放NO的能力设计一种新型人工血管支架材料。方法固载有机硒催化剂的聚乙烯亚胺( SePEI)作为聚阳离子,与聚阴离子聚谷氨酸(PGA)在静电纺丝得到的纳米纤维支架聚己内酯(PCL)表面层层自组装,用紫外和原子吸收进行了定性和定量的表征层层自组装结构;在还原型谷胱甘肽(GSH)的存在下测试材料催化分解NO供体亚硝基硫醇(RSNO)释放NO的能力,并进行相关生物性能的评价。结果材料对NO的催化释放过程相对稳定并且没有明显突释现象,80 h后仍能检测到NO产生。通过相关生物性能的检测,材料被证明基本没有毒性,并且在抗血小板凝聚方面具有显著作用。结论这种新型的血管支架材料在提高材料生物性能方面起到了很好的功效。%Objective A new style of artificial vessel scaffold was designed making the use of property of organoselenium catalyzing the releasing of Nitric oxide (NO). Methods Selenium-containing catalyst organoselenium immobilized polyethyleneimine (SePEI) as polycation and polyglutamic acid (PGA) as polyanion were alternately coated onto the surface of polycaprolactone (PCL) nanofiber scaffolds obtained by electrospinning to form the blood vessel scaffold. Self-assembly was characterized by UV and atomic absorption qualitatively and quantitatively. Catalytic generation of NO from the NO donors- RSNOs was tested under the existence of reducing agent RSH. Biological properties were also evaluated. Results The NO release was relatively stable with no significant burst appeared, and still could be detected after 80 hours of catalyzing. The material was proved to show little cytotoxicity, and displayed significant effect in inhibiting of platelet aggregation through biological testing. Conclusion The new style of artificial vessel scaffold has good effect on improving the biological properties of materials.

  20. Effect of Ozone Produced from Antibody-catalyzed Water Oxidation on Pathogenesis of Atherosclerosis

    Institute of Scientific and Technical Information of China (English)

    Ke-Jun PENG; Yu-Shan HUANG; Li-Na AN; Xiao-Qun HAN; Jing-Ge ZHANG; Qiu-Lin WANG; Jing SUN; Shu-Ren WANG

    2006-01-01

    Recent studies have suggested that antibodies can catalyze the generation of unknown oxidants including hydrogen peroxide (H2O2) and ozone (O3) from singlet oxygen (1O2) and water. This study is aimedto detect the effect of antibody-catalyzed water oxidation on atherosclerosis. Our results showed that both H2O2 and O3 were produced in human leukemia THP- 1 monocytes incubated with human immunoglobulin G and phorbol myristate acetate. In the THP-1 monocytes incubated with human immunoglobulin G, phorbol myristate acetate and low density lipoprotein, the intracellular total cholesterol, free cholesterol, cholesteryl ester and lipid peroxides clearly increased, and a larger number of foam cells were observed by oil red O staining. The accumulation of all intracellular lipids was significantly inhibited by vinylbenzoic acid, and only slightly affected by catalase. These findings suggested that the production of O3, rather than H2O2, might be involved in the pathogenesis of atherosclerosis through the antibody-catalyzed water oxidation pathway.

  1. A new approach for bio-jet fuel generation from palm oil and limonene in the absence of hydrogen.

    Science.gov (United States)

    Zhang, Jingjing; Zhao, Chen

    2015-12-18

    The traditional methodology includes a carbon-chain shortening strategy to produce bio-jet fuel from lipids via a two-stage process with hydrogen. Here, we propose a new solution using a carbon-chain filling strategy to convert C10 terpene and lipids to jet fuel ranged hydrocarbons with aromatic hydrocarbon ingredients in the absence of hydrogen.

  2. CuFe2 O4 -CuO Nanocomposites as Promising Materials for Solar Hydrogen Generation

    Science.gov (United States)

    Razavi, Mehdi; Amrollahi, Pouya; Yazdimamaghani, Mostafa; Tayebi, Lobat; Vashaee, Daryoosh

    2014-03-01

    Currently, hydrogen is produced, almost exclusively, by waterelectrolysis. This method can take advantage of economies of scale and most established techniques of producing hydrogen. We developed a nanocomposite material system composed of CuFe2O4 and CuO semiconductor particles to produce hydrogen by electrolysis of water. The nanocomposite powder was prepared using the sol-gel method. Techniques of X-ray diffraction, scanning electron microscopy with energy dispersive spectroscopy, transmission electron microscopy and UV diffuse reflectance analysis were employed to characterize the synthesized products.The results confirmed the formation of CuFe2O4-CuO nanocomposite powder. The hydrogen evolution was successfully observed over the new hetero-system of CuFe2O4-CuO. The electrolysis activity depended on the concentration of CuO in the system. In order to enhance the hydrogen production, we further optimized the composite material versus the concentration of the compounds.

  3. Sum Frequency Generation Vibrational Spectroscopy and Kinetic Study of 2-Methylfuran and 2,5-Dimethylfuran Hydrogenation over 7 nm Platinum Cubic Nanoparticles

    KAUST Repository

    Aliaga, Cesar

    2011-04-28

    Sum frequency generation vibrational spectroscopy and kinetic measurements obtained from gas chromatography were used to study the adsorption and hydrogenation of 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) over cubic Pt nanoparticles of 7 nm average size, synthesized by colloidal methods and cleaned by ultraviolet light and ozone treatment. Reactions carried out at atmospheric pressure in the temperature range of 20-120 °C produced dihydro and tetrahydro species, as well as ring-opening products (alcohols) and ring-cracking products, showing high selectivity toward ring opening throughout the entire temperature range. The aromatic rings (MF and DMF) adsorbed parallel to the nanoparticle surface. Results yield insight into various surface reaction intermediates and the reason for the significantly lower selectivity for ring cracking in DMF hydrogenation compared to MF hydrogenation. © 2011 American Chemical Society.

  4. Kinetics and mechanism of the oxidation of alkenes and silanes by hydrogen peroxide catalyzed by methylrhenium trioxide (MTO) and a novel application of electrospray mass spectrometry to study the hydrolysis of MTO

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Haisong

    1999-11-08

    Conjugated dienes were oxidized by hydrogen peroxide with methylrhenium trioxide (MTO) as catalyst. Methylrhenium bis-peroxide was the major reactive catalyst present. Hydroxyalkenes and trisubstituted silane were also tested. Mechanisms for each of these reactions are presented.

  5. Cooperative catalysis of metal and O-H···O/sp3-C-H···O two-point hydrogen bonds in alcoholic solvents: Cu-catalyzed enantioselective direct alkynylation of aldehydes with terminal alkynes.

    Science.gov (United States)

    Ishii, Takaoki; Watanabe, Ryo; Moriya, Toshimitsu; Ohmiya, Hirohisa; Mori, Seiji; Sawamura, Masaya

    2013-09-27

    Catalyst-substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand-substrate hydrogen-bonding interactions cooperate with a transition-metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol-based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum-mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp(3)-C-H···O hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst-substrate two-point hydrogen bonding.

  6. Palladium-Catalyzed Ullmann Cross-Coupling/Tandem Reductive Cyclization Route to Key Members of the Uleine Alkaloid Family.

    Science.gov (United States)

    Tang, Fei; Banwell, Martin G; Willis, Anthony C

    2016-04-01

    The trisubstituted cyclohexenone 12, generated through a palladium-catalyzed Ullmann cross-coupling reaction between o-iodonitrobenzene and a 4,5-trans-disubstituted 2-iodo-2-cyclohexen-1-one, engaged in a tandem reductive cyclization process upon exposure to hydrogen gas in the presence of Raney cobalt. As a result, the 1,5-methanoazocino[4,3-b]indole 13 was obtained and this could be readily elaborated to the racemic modifications of the alkaloids uleine, dasycarpidone, noruleine, and nordasycarpidone (1-4, respectively). PMID:26914482

  7. Development of a Novel Efficient Solid-Oxide Hybrid for Co-generation of Hydrogen and Electricity Using Nearby Resources for Local Application

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Greg, G.; Virkar, Anil, V.; Bandopadhyay, Sukumar; Thangamani, Nithyanantham; Anderson, Harlan, U.; Brow, Richard, K.

    2009-06-30

    Developing safe, reliable, cost-effective, and efficient hydrogen-electricity co-generation systems is an important step in the quest for national energy security and minimized reliance on foreign oil. This project aimed to, through materials research, develop a cost-effective advanced technology cogenerating hydrogen and electricity directly from distributed natural gas and/or coal-derived fuels. This advanced technology was built upon a novel hybrid module composed of solid-oxide fuel-assisted electrolysis cells (SOFECs) and solid-oxide fuel cells (SOFCs), both of which were in planar, anode-supported designs. A SOFEC is an electrochemical device, in which an oxidizable fuel and steam are fed to the anode and cathode, respectively. Steam on the cathode is split into oxygen ions that are transported through an oxygen ion-conducting electrolyte (i.e. YSZ) to oxidize the anode fuel. The dissociated hydrogen and residual steam are exhausted from the SOFEC cathode and then separated by condensation of the steam to produce pure hydrogen. The rationale was that in such an approach fuel provides a chemical potential replacing the external power conventionally used to drive electrolysis cells (i.e. solid oxide electrolysis cells). A SOFC is similar to the SOFEC by replacing cathode steam with air for power generation. To fulfill the cogeneration objective, a hybrid module comprising reversible SOFEC stacks and SOFC stacks was designed that planar SOFECs and SOFCs were manifolded in such a way that the anodes of both the SOFCs and the SOFECs were fed the same fuel, (i.e. natural gas or coal-derived fuel). Hydrogen was produced by SOFECs and electricity was generated by SOFCs within the same hybrid system. A stand-alone 5 kW system comprising three SOFEC-SOFC hybrid modules and three dedicated SOFC stacks, balance-of-plant components (including a tailgas-fired steam generator and tailgas-fired process heaters), and electronic controls was designed, though an overall

  8. Optimum hydrogen generation capacity and current density of the PEM-type water electrolyzer operated only during the off-peak period of electricity demand

    Science.gov (United States)

    Oi, Tsutomu; Sakaki, Yoshinori

    A requirement for widespread adoption of fuel cell vehicles in the transportation sector will be ready availability of pure hydrogen at prices that result in operating costs comparable to, or less than, that of gasoline internal combustion engine vehicles. The existing electrical power grid could be used as the backbone of the hydrogen infrastructure system in combination with water electrolyzers. A water electrolyzer can contribute to the load leveling by changing operational current density in accordance with the change of electricity demand. The optimum hydrogen generation capacity and current density of the polymer electrolyte membrane (PEM)-type water electrolyzer operated only during the off-peak period of electricity demand in respect of both the shortest time required for start and the higher efficiency of water electrolysis are obtained as 500 Nm 3 h -1 and 30 kA m -2, respectively. This PEM-type water electrolyzer could be used in the hydrogen refueling stations and energy storage systems constructed around hydrogen.

  9. Hydrogen utilization potential in subsurface sediments

    DEFF Research Database (Denmark)

    Adhikari, Rishi Ram; Glombitza, Clemens; Nickel, Julia;

    2016-01-01

    Subsurface microbial communities undertake many terminal electron-accepting processes, often simultaneously. Using a tritium-based assay, we measured the potential hydrogen oxidation catalyzed by hydrogenase enzymes in several subsurface sedimentary environments (Lake Van, Barents Sea, Equatorial...

  10. Tritium catalyzed deuterium tokamaks

    International Nuclear Information System (INIS)

    A preliminary assessment of the promise of the Tritium Catalyzed Deuterium (TCD) tokamak power reactors relative to that of deuterium-tritium (D-T) and catalyzed deuterium (Cat-D) tokamaks is undertaken. The TCD mode of operation is arrived at by converting the 3He from the D(D,n)3He reaction into tritium, by neutron capture in the blanket; the tritium thus produced is fed into the plasma. There are three main parts to the assessment: blanket study, reactor design and economic analysis and an assessment of the prospects for improvements in the performance of TCD reactors (and in the promise of the TCD mode of operation, in general)

  11. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-06-08

    Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate’s beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ~60°C, 80°C, and 95°C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal

  12. Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN3-Pincer Ligand

    KAUST Repository

    Pan, Yupeng

    2016-04-22

    An unsymmetrically protonated PN3-pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved. Grabbing hold: A PN3-pincer complex was employed for the selective hydrogen generation from formic acid. Mechanistic studies suggest the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. DECONTAMINATION ASSESSMENT OF BACILLUS ANTHRACIS, BACILLUS SUBTILIS, AND GEOBACILLUS STEAROTHERMOPHILUS SPORES ON INDOOR SURFACTS USING A HYDROGEN PERIOXIDE GAS GENERATOR

    Science.gov (United States)

    Aims: To evaluate the decontamination of Bacillus anthracis, Bacillus subtilis, and Geobacillus stearothermophilus spores on indoor surface materials using hydrogen peroxide gas. Methods and Results: B. anthracis, B. subtilis, and G. Stearothermophilus spores were dried on seven...

  14. Photoelectrochemical based direct conversion systems for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Kocha, S.; Peterson, M.; Arent, D. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    1996-10-01

    Photon driven, direct conversion systems consist of a light absorber and a water splitting catalyst as a monolithic system; water is split directly upon illumination. This one-step process eliminates the need to generate electricity externally and subsequently feed it to an electrolyzer. These configurations require only the piping necessary for transport of hydrogen to an external storage system or gas pipeline. This work is focused on multiphoton photoelectrochemical devices for production of hydrogen directly using sunlight and water. Two types of multijunction cells, one consisting of a-Si triple junctions and the other GaInP{sub 2}/GaAs homojunctions, were studied for the photoelectrochemical decomposition of water into hydrogen and oxygen from an aqueous electrolyte solution. To catalyze the water decomposition process, the illuminated surface of the device was modified either by addition of platinum colloids or by coating with ruthenium dioxide. These colloids have been characterized by gel electrophoresis.

  15. Design of a Metal Oxide-Organic Framework (MoOF) Foam Microreactor: Solar-Induced Direct Pollutant Degradation and Hydrogen Generation.

    Science.gov (United States)

    Zhu, Liangliang; Fu Tan, Chuan; Gao, Minmin; Ho, Ghim Wei

    2015-12-16

    A macroporous carbon network combined with mesoporous catalyst immobilization by a template method gives a metal-oxide-organic framework (MoOF) foam microreactor that readily soaks up pollutants and localizes solar energy in itself, leading to effective degradation of water pollutants (e.g., methyl orange (MO) and also hydrogen generation. The cleaned-up water can be removed from the microreactor simply by compression, and the microreactor used repeatedly. PMID:26501718

  16. Magnetic Co@g-C3N4 Core-Shells on rGO Sheets for Momentum Transfer with Catalytic Activity toward Continuous-Flow Hydrogen Generation.

    Science.gov (United States)

    Duan, Shasha; Han, Guosheng; Su, Yongheng; Zhang, Xiaoyu; Liu, Yanyan; Wu, Xianli; Li, Baojun

    2016-06-28

    Magnetic core-shell structures provide abundant opportunities for the construction of multifunctional composites. In this article, magnetic core-shells were fabricated with Co nanoparticles (NPs) as cores and g-C3N4 as shells. In the fabrication process, the Co@g-C3N4 core-shells were anchored onto the rGO nanosheets to form a Co@g-C3N4-rGO composite (CNG-I). For hydrogen generation from the hydrolysis of NaBH4 or NH3BH3, the Co NP cores act as catalytic active sites. The g-C3N4 shells protect Co NPs cores from aggregating or growing. The connection between Co NPs and rGO was strengthened by the g-C3N4 shells to prevent them from leaching or flowing away. The g-C3N4 shells also work as a cocatalyst for hydrogen generation. The magnetism of Co NPs and the shape of rGO nanosheets achieve effective momentum transfer in the external magnetic field. In the batch reactor, a higher catalytic activity was obtained for CNG-I in self-stirring mode than in magneton stirring mode. In the continuous-flow process, stable hydrogen generation was carried out with CNG-I being fixed and propelled by the external magnetic field. The separation film is unnecessary because of magnetic momentum transfer. This idea of the composite design and magnetic momentum transfer will be useful for the development of both hydrogen generation and multifunctional composite materials. PMID:27276187

  17. Design of a Metal Oxide-Organic Framework (MoOF) Foam Microreactor: Solar-Induced Direct Pollutant Degradation and Hydrogen Generation.

    Science.gov (United States)

    Zhu, Liangliang; Fu Tan, Chuan; Gao, Minmin; Ho, Ghim Wei

    2015-12-16

    A macroporous carbon network combined with mesoporous catalyst immobilization by a template method gives a metal-oxide-organic framework (MoOF) foam microreactor that readily soaks up pollutants and localizes solar energy in itself, leading to effective degradation of water pollutants (e.g., methyl orange (MO) and also hydrogen generation. The cleaned-up water can be removed from the microreactor simply by compression, and the microreactor used repeatedly.

  18. Effects of the large distribution of CdS quantum dot sizes on the charge transfer interactions into TiO2 nanotubes for photocatalytic hydrogen generation

    Science.gov (United States)

    González-Moya, Johan R.; Garcia-Basabe, Yunier; Rocco, Maria Luiza M.; Pereira, Marcelo B.; Princival, Jefferson L.; Almeida, Luciano C.; Araújo, Carlos M.; David, Denis G. F.; Ferreira da Silva, Antonio; Machado, Giovanna

    2016-07-01

    Hydrogen fuels generated by water splitting using a photocatalyst and solar irradiation are currently gaining the strength to diversify the world energy matrix in a green way. CdS quantum dots have revealed a hydrogen generation improvement when added to TiO2 materials under visible-light irradiation. In the present paper, we investigated the performance of TiO2 nanotubes coupled with CdS quantum dots, by a molecular bifunctional linker, on photocatalytic hydrogen generation. TiO2 nanotubes were obtained by anodization of Ti foil, followed by annealing to crystallize the nanotubes into the anatase phase. Afterwards, the samples were sensitized with CdS quantum dots via an in situ hydrothermal route using 3-mercaptopropionic acid as the capping agent. This sensitization technique permits high loading and uniform distribution of CdS quantum dots onto TiO2 nanotubes. The XPS depth profile showed that CdS concentration remains almost unchanged (homogeneous), while the concentration relative to the sulfate anion decreases by more than 80% with respect to the initial value after ∼100 nm in depth. The presence of sulfate anions is due to the oxidation of sulfide and occurs in greater proportion in the material surface. This protection for air oxidation inside the nanotubular matrix seemingly protected the CdS for photocorrosion in sacrificial solution leading to good stability properties proved by long duration, stable photocurrent measurements. The effect of the size and the distribution of sizes of CdS quantum dots attached to TiO2 nanotubes on the photocatalytic hydrogen generation were investigated. The experimental results showed three different behaviors when the reaction time of CdS synthesis was increased in the sensitized samples, i.e. similar, deactivation and activation effects on the hydrogen production with regard to TiO2 nanotubes. The deactivation effect was related to two populations of sizes of CdS, where the population with a shorter band gap acts as a

  19. Improved Hydrogen Gas Getters for TRU Waste -- Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Mark Stone; Michael Benson; Christopher Orme; Thomas Luther; Eric Peterson

    2005-09-01

    Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage containers. For that reason, the Nuclear Regulatory Commission limits the flammable gas (hydrogen) concentration in the Transuranic Package Transporter-II (TRUPACT-II) containers to 5 vol% of hydrogen in air, which is the lower explosion limit. Consequently, a method is needed to prevent the build up of hydrogen to 5 vol% during the storage and transport of the TRUPACT-II containers (up to 60 days). One promising option is the use of hydrogen getters. These materials scavenge hydrogen from the gas phase and irreversibly bind it in the solid phase. One proven getter is a material called 1,4-bis (phenylethynyl) benzene, or DEB, characterized by the presence of carbon-carbon triple bonds. Carbon may, in the presence of suitable precious metal catalysts such as palladium, irreversibly react with and bind hydrogen. In the presence of oxygen, the precious metal may also eliminate hydrogen by catalyzing the formation of water. This reaction is called catalytic recombination. DEB has the needed binding rate and capacity for hydrogen that potentially could be generated in the TRUPACT II. Phases 1 and 2 of this project showed that uncoated DEB performed satisfactorily in lab scale tests. Based upon these results, Phase 3, the final project phase, included larger scale testing. Test vessels were scaled to replicate the ratio between void space in the inner containment vessel of a TRUPACT-II container and a payload of seven 55-gallon drums. The tests were run with an atmosphere of air for 63.9 days at ambient temperature (15-27°C) and a scaled hydrogen generation rate of 2.60E-07 moles per second (0.35 cc/min). A second type of getter known as VEI, a proprietary polymer hydrogen getter characterized by carbon-carbon double bonds, was also tested in Phase 3. Hydrogen was successfully “gettered” by both getter systems. Hydrogen concentrations remained below 5 vol% (in

  20. Influence of hydrogen bonding on the generation and stabilization of liquid crystalline polyesters, poly(esteramide)s and polyacrylates

    Indian Academy of Sciences (India)

    C K S Pillai; K Y Sandhya; J D Sudha; M Saminathan

    2003-08-01

    Induction and stabilization of liquid crystallinity through hydrogen bonding (HB) are now well-established. Interesting observations made on the influence of HB on LC behaviour of amido diol-based poly(esteramide)s, poly(esteramide)s containing nitro groups and azobenzene mesogen-based polyacrylates will be discussed. The use of amido diol as an important precursor for the synthesis of novel PEAs containing inbuilt di-amide linkage enabled generation of extensive hydrogen bondings between the amide–amide and amide–ester groups which stabilized the mesophase structures of the PEAs. The contributions of hydrogen bonding to the generation and stabilization of mesophase structures were plainly evident from the observation of liquid crystallinity even in PEAs prepared from fully aliphatic amido diols. Replacement of terephthaloyl units by isophthaloyl moiety totally vanquished liquid crystalline phases while biphenylene and naphthalene units did only reduce the transition temperatures as expected. The occurrence of the smectic phases in some of the polymers indicated possibly self-assembly through the formation of hetero intermolecular hydrogen bonded networks. A smectic polymorphism and in addition, a smectic-to-nematic transition, were observed in the monomers and polymers based on 1,4-phenylene[bis-(3-nitroanthranilidic acid)] containing nitro groups. A smectic polymorphism was also observed as a combined effect of hydrogen bonded carboxyl groups and laterally substituted alkyl side chains in the case of azobenzene mesogen containing side chain polyacrylates. It was further shown that the presence of the mesophase enhances the non-linear optical (NLO) response of these polymers.

  1. 苯乙胺衍生的手性膦-亚磷酰胺酯配体在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中的应用%Rh-Catalyzed Asymmetric Hydrogenation of α-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine-Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平

    2012-01-01

    A series of phosphine-phosphoramidite ligands derived from commercially available,inexpensive chiral 1-phenylethylamine were employed in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates.The results indicated that the ligand(Sc,Sa)-2b bearing a Me-group on amino moiety exhibited similar enantioselectivity but superior catalytic activity to(Rc,Ra)-THNAPhos.Excellent enantioselectivities(up to 99% ee) and high catalytic activity(S/C up to 5 000) have been achieved in the hydrogenation of various β-alkyl and β-aryl substituted substrates,demonstrating the high potential of this phosphine-phosphoramidite ligand in the preparation of optically active α-hydroxyphosphonates%将苯乙胺衍生的手性膦-亚磷酰胺酯配体应用在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性最高〉99%ee.

  2. HYDROGEN GENERATION FROM SLUDGE SAMPLE BOTTLES CAUSED BY RADIOLYSIS AND CHEMISTRY WITH CONCETNRATION DETERMINATION IN A STANDARD WASTE BOX (SWB) OR DRUM FOR TRANSPORT

    Energy Technology Data Exchange (ETDEWEB)

    RILEY DL; BRIDGES AE; EDWARDS WS

    2010-03-30

    A volume of 600 mL of sludge, in 4.1 L sample bottles (Appendix 7.6), will be placed in either a Super Pig (Ref. 1) or Piglet (Ref. 2, 3) based on shielding requirements (Ref. 4). Two Super Pigs will be placed in a Standard Waste Box (SWB, Ref. 5), as their weight exceeds the capacity of a drum; two Piglets will be placed in a 55-gallon drum (shown in Appendix 7.2). The generation of hydrogen gas through oxidation/corrosion of uranium metal by its reaction with water will be determined and combined with the hydrogen produced by radiolysis. The hydrogen concentration in the 55-gallon drum and SWB will be calculated to show that the lower flammability limit of 5% hydrogen is not reached. The inner layers (i.e., sample bottle, bag and shielded pig) in the SWB and drum will be evaluated to assure no pressurization occurs as the hydrogen vents from the inner containers (e.g., shielded pigs, etc.). The reaction of uranium metal with anoxic liquid water is highly exothermic; the heat of reaction will be combined with the source term decay heat, calculated from Radcalc, to show that the drum and SWB package heat load limits are satisfied. This analysis does five things: (1) Estimates the H{sub 2} generation from the reaction of uranium metal with water; (2) Estimates the H{sub 2} generation from radiolysis (using Radcalc 4.1); (3) Combines both H{sub 2} generation amounts, from Items 1 and 2, and determines the percent concentration of H{sub 2} in the interior of an SWB with two Super Pigs, and the interior of a 55-gallon drum with two Piglets; (4) From the combined gas generation rate, shows that the pressure at internal layers is minimal; and (5) Calculates the maximum thermal load of the package, both from radioactive decay of the source and daughter products as calculated/reported by Radcalc 4.1, and from the exothermic reaction of uranium metal with water.

  3. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.

    2012-06-29

    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  4. Spin Trapping of the Phosphorus-centered Radicals Generated from Hydrogen Abstraction Reaction by 2,2-Diphenyl-1-picrylhydrazyl

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Two kinds of the phosphorus-centered radicals produced from hydrogen atom abstraction by2,2-diphenyl-1-picrylhydrazyl (DPPH) were trapped by N-tert-butyl-a-phenylnitrone (PBN) and5,5-dimethyl-l-pyrroline N-oxide (DMPO), and investigated by means of EPR spectroscopy.The spin adducts with a characteristic hyperfine coupling constant(hfcc) caused by a phosphorusatom were observed. Based on the hfcc values caused by the phosphorus and hydrogen atoms,the conformational positions of the adducts trapped by PBN and DMPO are discussed.

  5. Density functional theory (DFT) on CO2 hydrogenation catalyzed by TiO reaction mechanism in the gas phase%气相中 TiO 催化 CO2加氢的两态反应密度泛函理论研究

    Institute of Scientific and Technical Information of China (English)

    王永成; 王文雪; 马盼盼

    2015-01-01

    为了说明两态反应会影响甚至决定整个反应的反应速率或选择性,运用密度泛函(DFT )B3lyp/6‐311+ G (3df ,2p)方法,对TiO催化CO2加氢生成甲酸反应的单、三重态各个驻点结构进行优化。发现在两个自旋态势能面之间有四处能量交叉点(CPs),由此找出最低能量交叉点(MECP),根据交叉点的构型计算自旋‐轨道耦合(SOC)常数,用Landau‐Zener非绝热跃迁公式计算出M ECP处的跃迁几率,发现四处最低能量交叉点都具有较强的自旋‐轨道耦合作用和较高的跃迁几率,且四个最低能量交叉点处电子的自旋翻转均发生在Ti原子不同的d轨道之间,确定了最低能量反应路径。用能量跨度模型计算了在298 K下TiO的转化频率(TOF)及整个过程的控制度(XTOF ),同时确定了整个反应过程中的决速态。%To illustrate the two state reaction will influence and even determine the reaction rate of the whole or selectivity ,the density functional method(DFT) B3lyp/6‐311+ G(3df ,2p) is used to optimize CO2 hydrogenation to generate formate catalyzed by TiO of singlet and triplet stagnation point structure in the gas phase .Under the whole catalytic cycle ,there are four crossing points between singlet and triplet potential energy surfaces . T he possibilities of spin flip at M ECPs are discussed through spin‐orbit coupling calculations . T he electron transition probability are calculated by Landau‐Zener formula , 4 M ECPs has strong spin‐orbit coupling effect and higher transition probability , and all spin inversion is occurred in different d orbits of titanium . Finally , the lowest energy reaction path is ensured . The turnover frequency(TOF) and XTOF at 298 K have been obtained by citing the energetic span model proposed by Kozuch . T he fast mode in the process of reaction is determined .

  6. Law proposal aiming at imposing the domestic consumption tax to the natural gas used for hydrogen generation for petroleum refining purposes; Proposition de loi visant a soumettre a la taxe interieure de consommation le gaz naturel utilise pour la production d'hydrogene a des fins de raffinage petrolier

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2009-04-15

    In France, natural gas benefits from tax exemptions in several situations and in particular when used as raw material for hydrogen generation, which in turn, is used for crude oil refining and fuels generation. However, crude oil is cheaper when it is heavier but more hydrogen, and thus more natural gas, is needed to refine it and more CO{sub 2} is released in the atmosphere. Therefore, refining cheap crude oil increases the refining margins of oil companies but their environmental impact as well. The aim of this law proposal is to impose the domestic consumption tax to natural gas when used in oil refining processes in order to finance the development of the renewable hydrogen industry through the creation of a High Council of Hydrogen Industry. This High Council would be in charge of promoting the development of renewable hydrogen production facilities and distribution circuits, of hydrogen-fueled vehicles, and of fuel cells. (J.S.)

  7. An Amorphous Carbon Nitride Photocatalyst with Greatly Extended Visible-Light-Responsive Range for Photocatalytic Hydrogen Generation.

    Science.gov (United States)

    Kang, Yuyang; Yang, Yongqiang; Yin, Li-Chang; Kang, Xiangdong; Liu, Gang; Cheng, Hui-Ming

    2015-08-19

    Amorphous carbon nitride (ACN) with a bandgap of 1.90 eV shows an order of magnitude higher photocatalytic activity in hydrogen evolution under visible light than partially crystalline graphitic carbon nitride with a bandgap of 2.82 eV. ACN is photocatalytically active under visible light at a wavelength beyond 600 nm.

  8. Inclusion of preferential diffusion in simulations of premixed combustion of hydrogen/methane mixtures with flamelet generated manifolds

    NARCIS (Netherlands)

    Swart, J.A.M.de; Bastiaans, R.J.M.; Oijen, J.A. van; Goey, L.P.H. de; Cant, R.S.

    2010-01-01

    In this paper we study the possibility to account for preferential diffusion effects in lean turbulent premixed flames in numerical predictions with reduced chemistry. We studied the situation when hydrogen is added to methane at levels of 20% and 40% by volume in the fuel, at lean combustion (φ= 0.

  9. Photo-stability of a-Si solar cells fabricated by “Liquid-Si printing method” and treated with catalytic generated atomic hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Murayama, Hiroko, E-mail: murayama.hiroko5@jp.panasonic.com [Device Solutions Center, Panasonic Corporation, 3-1-1 Yagumo-naka-machi, Moriguchi City, Osaka 570-8501 (Japan); Ohyama, Tatsushi; Yoshida, Isao; Terakawa, Akira [Device Solutions Center, Panasonic Corporation, 3-1-1 Yagumo-naka-machi, Moriguchi City, Osaka 570-8501 (Japan); Masuda, Takashi [Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi City, Ishikawa 923-1292 (Japan); JST-ERATO Shimoda Nano-Liquid Process Project, 1-1 Asahidai, Nomi City, Ishikawa 923-1292 (Japan); Ohdaira, Keisuke [Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi City, Ishikawa 923-1292 (Japan); Shimoda, Tatsuya [Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi City, Ishikawa 923-1292 (Japan); JST-ERATO Shimoda Nano-Liquid Process Project, 1-1 Asahidai, Nomi City, Ishikawa 923-1292 (Japan)

    2015-01-30

    The film properties and solar cell performances of hydrogenated amorphous silicon (a-Si:H) fabricated by a newly developed non-vacuum process “Liquid-Si printing method” were systematically investigated by comparing to the conventional plasma-chemical vapor deposition method. The as-printed a-Si:H films showed relatively high Urbach-tail characteristic energy (E{sub ch}), high [Si–H{sub 2}]/[Si–H], and low photoconductivity (~ 10{sup −7} S/cm). However, the [Si–H{sub 2}]/[Si–H] decreased, and the photoconductivity was improved to the device grade level (~ 10{sup −5} S/cm) after appropriate catalytic-generated atomic hydrogen treatment. It was also found that the light-induced degradation of the photoconductivity and solar cell efficiency of the printed samples were less than half of the conventional a-Si:H case.

  10. Photo-stability of a-Si solar cells fabricated by “Liquid-Si printing method” and treated with catalytic generated atomic hydrogen

    International Nuclear Information System (INIS)

    The film properties and solar cell performances of hydrogenated amorphous silicon (a-Si:H) fabricated by a newly developed non-vacuum process “Liquid-Si printing method” were systematically investigated by comparing to the conventional plasma-chemical vapor deposition method. The as-printed a-Si:H films showed relatively high Urbach-tail characteristic energy (Ech), high [Si–H2]/[Si–H], and low photoconductivity (~ 10−7 S/cm). However, the [Si–H2]/[Si–H] decreased, and the photoconductivity was improved to the device grade level (~ 10−5 S/cm) after appropriate catalytic-generated atomic hydrogen treatment. It was also found that the light-induced degradation of the photoconductivity and solar cell efficiency of the printed samples were less than half of the conventional a-Si:H case

  11. Global model analysis of negative ion generation in low-pressure inductively coupled hydrogen plasmas with bi-Maxwellian electron energy distributions

    International Nuclear Information System (INIS)

    A global model was developed to investigate the densities of negative ions and the other species in a low-pressure inductively coupled hydrogen plasma with a bi-Maxwellian electron energy distribution. Compared to a Maxwellian plasma, bi-Maxwellian plasmas have higher populations of low-energy electrons and highly vibrationally excited hydrogen molecules that are generated efficiently by high-energy electrons. This leads to a higher reaction rate of the dissociative electron attachment responsible for negative ion production. The model indicated that the bi-Maxwellian electron energy distribution at low pressures is favorable for the creation of negative ions. In addition, the electron temperature, electron density, and negative ion density calculated using the model were compared with the experimental data. In the low-pressure regime, the model results of the bi-Maxwellian electron energy distributions agreed well quantitatively with the experimental measurements, unlike those of the assumed Maxwellian electron energy distributions that had discrepancies

  12. 浅析330MW发电机漏氢原因与防范措施%Analysis of Hydrogen Leakage Causes and Preventive Measures of 330MW Generator

    Institute of Scientific and Technical Information of China (English)

    朱敬伟

    2015-01-01

    The hydrogen leakage amount (rate) of hydrogen-cooled turbo generator directly affects the safety and economic operation of generator, and the amount (rate) of hydrogen leakage is one of the major technical indicators of the operation of turbo generator and an important indicator of the safety evaluation of generator. This article focuses on the cause analysis and preventive measures of excessive hydrogen content of two domestic 330MW generator stator cooling water tank in Datang Jilin Hunchun power generation plant and the methods to control the hydrogen leakage of 330MW hydrogen-cooled generator.%氢内冷汽轮发电机漏氢量(率)的大小直接影响发电机的安全、经济运行,漏氢量(率)是汽轮发电机组运行的主要技术指标之一,也是发电机安全性评价的一个重要指标。本文着重介绍了大唐吉林珲春发电厂运行的产两台国产330MW发电机定冷水箱含氢量超标的原因分析和防范措施以及治理330MW氢内冷发电机漏氢的方法。

  13. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  14. Can Contemporary Density Functional Theory Predict Energy Spans in Molecular Catalysis Accurately Enough To Be Applicable for in Silico Catalyst Design? A Computational/Experimental Case Study for the Ruthenium-Catalyzed Hydrogenation of Olefins.

    Science.gov (United States)

    Rohmann, Kai; Hölscher, Markus; Leitner, Walter

    2016-01-13

    The catalytic hydrogenation of cyclohexene and 1-methylcyclohexene is investigated experimentally and by means of density functional theory (DFT) computations using novel ruthenium Xantphos(Ph) (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) and Xantphos(Cy) (4,5-bis(dicyclohexylphosphino)-9,9-dimethylxanthene) precatalysts [Ru(Xantphos(Ph))(PhCO2)(Cl)] (1) and [Ru(Xantphos(Cy))(PhCO2)(Cl)] (2), the synthesis, characterization, and crystal structures of which are reported. The intention of this work is to (i) understand the reaction mechanisms on the microscopic level and (ii) compare experimentally observed activation barriers with computed barriers. The Gibbs free activation energy ΔG(⧧) was obtained experimentally with precatalyst 1 from Eyring plots for the hydrogenation of cyclohexene (ΔG(⧧) = 17.2 ± 1.0 kcal/mol) and 1-methylcyclohexene (ΔG(⧧) = 18.8 ± 2.4 kcal/mol), while the Gibbs free activation energy ΔG(⧧) for the hydrogenation of cyclohexene with precatalyst 2 was determined to be 21.1 ± 2.3 kcal/mol. Plausible activation pathways and catalytic cycles were computed in the gas phase (M06-L/def2-SVP). A variety of popular density functionals (ωB97X-D, LC-ωPBE, CAM-B3LYP, B3LYP, B97-D3BJ, B3LYP-D3, BP86-D3, PBE0-D3, M06-L, MN12-L) were used to reoptimize the turnover determining states in the solvent phase (DF/def2-TZVP; IEF-PCM and/or SMD) to investigate how well the experimentally obtained activation barriers can be reproduced by the calculations. The density functionals B97-D3BJ, MN12-L, M06-L, B3LYP-D3, and CAM-B3LYP reproduce the experimentally observed activation barriers for both olefins very well with very small (0.1 kcal/mol) to moderate (3.0 kcal/mol) mean deviations from the experimental values indicating for the field of hydrogenation catalysis most of these functionals to be useful for in silico catalyst design prior to experimental work. PMID:26713773

  15. Facile synthesis of near-monodisperse Ag-Ni core-shell nanoparticles and their application for catalytic generation of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Guo Huizhang; Chen Yuanzhi; Chen Xiaozhen; Wen Ruitao; Yue Guanghui; Peng Dongliang, E-mail: yuanzhi@xmu.edu.cn, E-mail: dlpeng@xmu.edu.cn [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China)

    2011-05-13

    Magnetically recyclable Ag-Ni core-shell nanoparticles have been fabricated via a simple one-pot synthetic route using oleylamine both as solvent and reducing agent and triphenylphosphine as a surfactant. As characterized by transmission electron microscopy (TEM), the as-synthesized Ag-Ni core-shell nanoparticles exhibit a very narrow size distribution with a typical size of 14.9 {+-} 1.2 nm and a tunable shell thickness. UV-vis absorption spectroscopy study shows that the formation of a Ni shell on Ag core can damp the surface plasmon resonance (SPR) of the Ag core and lead to a red-shifted SPR absorption peak. Magnetic measurement indicates that all the as-synthesized Ag-Ni core-shell nanoparticles are superparamagnetic at room temperature, and their blocking temperatures can be controlled by modulating the shell thickness. The as-synthesized Ag-Ni core-shell nanoparticles exhibit excellent catalytic properties for the generation of H{sub 2} from dehydrogenation of sodium borohydride in aqueous solutions. The hydrogen generation rate of Ag-Ni core-shell nanoparticles is found to be much higher than that of Ag and Ni nanoparticles of a similar size, and the calculated activation energy for hydrogen generation is lower than that of many bimetallic catalysts. The strategy employed here can also be extended to other noble-magnetic metal systems.

  16. MOLYBDENUM CATALYZED ACID PEROXIDE BLEACHING OF EUCALYPTUS KRAFT PULP

    Directory of Open Access Journals (Sweden)

    Marcos S. Rabelo

    2008-08-01

    Full Text Available Molybdenum catalyzed peroxide bleaching (PMo Stage consists of pulp treatment with hydrogen peroxide under acidic conditions in the presence of a molybdenum catalyst. Molybdenum is applied in catalytic doses (50-200 mg/kg pulp and may originate from various sources, including (NH46Mo7O24.4H2O, Na2MoO4.2H2O, siliconmolybdate, etc. This work is aimed at optimizing the PMo stage and evaluating its industrial application in the OAZDP sequence. Optimum PMo stage conditions for bleaching eucalyptus pulp were 90 ºC, pH 3.5, 2 h, 0.1 kg/adt Mo and 5 kg/adt H2O2. The PMo stage was more efficient to remove pulp hexenuronic acids than lignin. Its efficiency decreased with increasing pH in the range of 1.5-5.5, while it increased with increasing temperature and peroxide and molybdenum doses. The application of the PMo stage as replacement for the A-stage of the AZDP sequence significantly decreased chlorine dioxide demand. The PMo stage caused a decrease of 20-30% in the generation of organically bound chlorine. The quality parameters of the pulp produced during the PMo stage mill trial were comparable to those obtained with the reference A-stage.

  17. Structure and performance of cobalt and nickel catalysts for hydrogen generation from bio-ethanol partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Ehrlich, Heike; Kraleva, Elka [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse

    2012-07-01

    A hydrogen and CO rich fuel gas used for SOFC applications is obtained directly from ethanol by partial oxidation. Low-cost cobalt and nickel metals supported on different mixed oxides were found to be highly active catalysts in this reaction. The ethanol conversion started above 350 C and increased with increasing reaction temperature. Hydrogen and carbon monoxide were the predominant products at temperatures above 500 C. Among the catalysts studied, CoAlZn and NiAlZn mixed oxides showed to provide the highest H{sub 2} and CO selectivity. By the use of a sol-gel method for catalyst preparation the drawback of oxide sintering at high temperature could be eliminated. It was found that phase composition of the catalysts and their thermal stability depends significantly on the preparation method and chemical composition. (orig.)

  18. Reduction of pollutants and disinfection of industrial wastewater by an integrated system of copper electrocoagulation and electrochemically generated hydrogen peroxide.

    Science.gov (United States)

    Barrera-Díaz, Carlos E; Frontana-Uribe, Bernardo A; Roa-Morales, Gabriela; Bilyeu, Bryan W

    2015-01-01

    The objective of this study was to evaluate the effect of copper electrocoagulation and hydrogen peroxide on COD, color, turbidity, and bacterial activity in a mixed industry wastewater. The integrated system of copper electrocoagulation and hydrogen peroxide is effective at reducing the organic and bacterial content of industrial wastewater. The copper electrocoagulation alone reduces COD by 56% in 30 min at pH 2.8, but the combined system reduces COD by 78%, biochemical oxygen demand (BOD5) by 81%, and color by 97% under the same conditions. Colloidal particles are flocculated effectively, as shown by the reduction of zeta potential and the 84% reduction in turbidity and 99% reduction in total solids. Additionally, the total coliforms, fecal coliforms, and bacteria are all reduced by 99%. The integrated system is effective and practical for the reduction of both organic and bacterial content in industrial wastewater.

  19. Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

    Science.gov (United States)

    Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

    2016-07-01

    Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane. PMID:27302302

  20. Catalytic Hydrolysis of Ammonia Borane by Cobalt Nickel Nanoparticles Supported on Reduced Graphene Oxide for Hydrogen Generation

    Directory of Open Access Journals (Sweden)

    Yuwen Yang

    2014-01-01

    Full Text Available Well dispersed magnetically recyclable bimetallic CoNi nanoparticles (NPs supported on the reduced graphene oxide (RGO were synthesized by one-step in situ coreduction of aqueous solution of cobalt(II chloride, nickel (II chloride, and graphite oxide (GO with ammonia borane (AB as the reducing agent under ambient condition. The CoNi/RGO NPs exhibits excellent catalytic activity with a total turnover frequency (TOF value of 19.54 mol H2 mol catalyst−1 min−1 and a low activation energy value of 39.89 kJ mol−1 at room temperature. Additionally, the RGO supported CoNi NPs exhibit much higher catalytic activity than the monometallic and RGO-free CoNi counterparts. Moreover, the as-prepared catalysts exert satisfying durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB, which make the practical reusing application of the catalysts more convenient. The usage of the low-cost, easy-getting catalyst to realize the production of hydrogen under mild condition gives more confidence for the application of ammonia borane as a hydrogen storage material. Hence, this general method indicates that AB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other RGO-based metallic systems.