WorldWideScience

Sample records for catalyzed hydrogen generation

  1. Removal of SU-8 resists using hydrogen radicals generated by tungsten hot-wire catalyzer

    Science.gov (United States)

    Kono, Akihiko; Arai, Yu; Goto, Yousuke; Horibe, Hideo

    2012-03-01

    We investigated removal of chemically amplified negative-tone i-line resist SU-8 using hydrogen radicals, which was generated by the catalytic decomposition of H2/N2 mixed gas (H2:N2 = 10:90vol.%) using tungsten hot-wire catalyzer. SU-8 with exposure dose from 7 (Dg100×0.5) to 280mJ/cm2 (Dg100×20) were removed by hydrogen radicals without a residual layer. When the distance between the catalyzer and the substrate was 100mm, the catalyzer temperature was 2400°C, and the initial substrate temperature was 50°C, removal rate of SU-8 was 0.17μm/min independent of exposure dose to the SU-8. Finally, we obtained high removal rate for SU-8 (exposure dose = 14mJ/cm2 (Dg100)) of approximately 4μm/min when the distance between the catalyzer and the substrate was 20mm, the catalyzer temperature was 2400°C, and the initial substrate temperature was 165°C.

  2. High removal rate of cross-linked SU-8 resist using hydrogen radicals generated by tungsten hot-wire catalyzer

    Energy Technology Data Exchange (ETDEWEB)

    Kono, Akihiko, E-mail: a.kono@neptune.kanazawa-it.ac.jp [Kanazawa Institute of Technology, 7-1 Ougigaoka, Nonoichi, Ishikawa 921-8501 (Japan); Arai, Yu; Maruoka, Takeshi; Yamamoto, Masashi; Goto, Yousuke; Takahashi, Seiji; Nishiyama, Takashi [Kanazawa Institute of Technology, 7-1 Ougigaoka, Nonoichi, Ishikawa 921-8501 (Japan); Horibe, Hideo [Osaka City University, Sugimoto, Sumiyoshiku, Osaka 558-8585 (Japan)

    2014-07-01

    This paper discusses the removal of chemically amplified negative-tone i-line resist SU-8 using hydrogen radicals generated by the catalytic decomposition of H{sub 2} molecules in H{sub 2}/N{sub 2} mixed gas (H{sub 2}:N{sub 2} = 10:90 vol.%) using a tungsten hot-wire catalyzer. SU-8 resists with exposure doses from 7 to 280 mJ/cm{sup 2} were removed by hydrogen radicals, although the SU-8 removal rate was independent of the exposure dose. The SU-8 removal rate increased with both substrate and catalyzer temperature, in addition to a decrease in the distance between the catalyzer and substrate. A high removal rate for cross-linked SU-8 with an exposure dose of 14 mJ/cm{sup 2} of approximately 4 μm/min was achieved with a catalyzer to substrate distance of 20 mm, and catalyzer and initial substrate temperatures of 2400 and 165 °C, respectively. - Highlights: • Chemically amplified negative-tone i-line resist SU-8 removed by hydrogen radicals • Hydrogen radicals generated by catalytic H{sub 2} decomposition using hot-wire catalyzer • The cross-linked SU-8 resist was removed at a rate of approximately 4 μm/min.

  3. Laboratory Studies of Hydrogen Gas Generation Using the Cobalt Chloride Catalyzed Sodium Borohydride-Water Reaction

    Science.gov (United States)

    2015-07-01

    is a plot of total hydrogen gas as a function of reaction time. This experiment was conducted in the pressure tank at an applied pressure of 13 psig...function of reaction time. This experiment was conducted in the pressure tank at an applied pressure of 50 psig using a H2O:NaBH4 ratio of 4.6:1 and 3.0... pressure tank (McMaster-Carr, part number. 6778K21). The pressure tank has a 185-psig maximum pressure rating at 37.8 ºC and a maximum operating

  4. 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.

  5. Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes.

    Science.gov (United States)

    Li, Meina; Kong, Duanyang; Zi, Guofu; Hou, Guohua

    2017-01-06

    A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.

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

    OpenAIRE

    Honggang Chang; Ronghai Zhu; Zongshe Liu; Jinlong He; Chongrong Wen; Sujuan Zhang; Yang Li

    2015-01-01

    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, prepar...

  7. 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

  8. 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.

  9. 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.

  10. Diastereoselective Hydrogenation and Kinetic Resolution of Imines Using Rhodium/Diphosphine Catalyzed Hydrogenation.

    NARCIS (Netherlands)

    Lensink, Cornelis; Vries, Johannes G. de

    1993-01-01

    Kinetic resolution of racemic α-methylbenzyl amine can be achieved with 98% ee. of the remaining amine at 70% conversion using the Rhodium/2S,4S-BDPP catalyzed asymmetric hydrogenation of imines. The same catalyst will hydrogenate optically pure α-methylbenzyl amines with a diastereoselectivity of u

  11. 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

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

    2004-01-01

    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 N2, H2, O2 and NH3 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, NH2 (~3325 cm-1) and NH (~3235 cm-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° 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°. 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.

  13. 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.

  14. 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%.

  15. 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.)

  16. 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

  17. Simulation of hydrogen and hydrogen-assisted propane ignition in Pt catalyzed microchannel

    Energy Technology Data Exchange (ETDEWEB)

    Seshadri, Vikram; Kaisare, Niket S. [Department of Chemical Engineering, Indian Institute of Technology - Madras, Chennai 600 036 (India)

    2010-11-15

    This paper deals with self-ignition of catalytic microburners from ambient cold-start conditions. First, reaction kinetics for hydrogen combustion is validated with experimental results from the literature, followed by validation of a simplified pseudo-2D microburner model. The model is then used to study the self-ignition behavior of lean hydrogen/air mixtures in a Platinum-catalyzed microburner. Hydrogen combustion on Pt is a very fast reaction. During cold start ignition, hydrogen conversion reaches 100% within the first few seconds and the reactor dynamics are governed by the ''thermal inertia'' of the microburner wall structure. The self-ignition property of hydrogen can be used to provide the energy required for propane ignition. Two different modes of hydrogen-assisted propane ignition are considered: co-feed mode, where the microburner inlet consists of premixed hydrogen/propane/air mixtures; and sequential feed mode, where the inlet feed is switched from hydrogen/air to propane/air mixtures after the microburner reaches propane ignition temperature. We show that hydrogen-assisted ignition is equivalent to selectively preheating the inlet section of the microburner. The time to reach steady state is lower at higher equivalence ratio, lower wall thermal conductivity, and higher inlet velocity for both the ignition modes. The ignition times and propane emissions are compared. Although the sequential feed mode requires slightly higher amount of hydrogen, the propane emissions are at least an order of magnitude lower than the other ignition modes. (author)

  18. 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 ℃.

  19. 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.

  20. Hydrogen evolution catalyzed by cobalt diimine-dioxime complexes.

    Science.gov (United States)

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-05-19

    Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged 10 years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, that is, close to the thermodynamic equilibrium over a wide range of acid-base conditions in nonaqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly, we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts in the

  1. 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.

  2. 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.

  3. Cobalt-catalyzed hydrogenation of esters to alcohols: unexpected reactivity trend indicates ester enolate intermediacy.

    Science.gov (United States)

    Srimani, Dipankar; Mukherjee, Arup; Goldberg, Alexander F G; Leitus, Gregory; Diskin-Posner, Yael; Shimon, Linda J W; Ben David, Yehoshoa; Milstein, David

    2015-10-12

    The atom-efficient and environmentally benign catalytic hydrogenation of carboxylic acid esters to alcohols has been accomplished in recent years mainly with precious-metal-based catalysts, with few exceptions. Presented here is the first cobalt-catalyzed hydrogenation of esters to the corresponding alcohols. Unexpectedly, the evidence indicates the unprecedented involvement of ester enolate intermediates.

  4. 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.

  5. Nanostructured Ti-catalyzed MgH2 for hydrogen storage.

    Science.gov (United States)

    Shao, H; Felderhoff, M; Schüth, F; Weidenthaler, C

    2011-06-10

    Nanocrystalline Ti-catalyzed MgH(2) can be prepared by a homogeneously catalyzed synthesis method. Comprehensive characterization of this sample and measurements of hydrogen storage properties are discussed and compared to a commercial MgH(2) sample. The catalyzed MgH(2) nanocrystalline sample consists of two MgH(2) phases-a tetrahedral β-MgH(2) phase and an orthorhombic high-pressure modification γ-MgH(2). Transmission electron microscopy was used for the observation of the morphology of the samples and to confirm the nanostructure. N(2) adsorption measurement shows a BET surface area of 108 m(2) g(-1) of the nanostructured material. This sample exhibits a hydrogen desorption temperature more than 130 °C lower compared to commercial MgH(2). After desorption, the catalyzed nanocrystalline sample absorbs hydrogen 40 times faster than commercial MgH(2) at 300 °C. Both the Ti catalyst and the nanocrystalline structure with correspondingly high surface area are thought to play important roles in the improvement of hydrogen storage properties. The desorption enthalpy and entropy values of the catalyzed MgH(2) nanocrystalline sample are 77.7 kJ mol(-1) H(2) and 138.3 J K(-1) mol(-1) H(2), respectively. Thermodynamic properties do not change with the nanostructure.

  6. 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...

  7. Bifunctional Asymmetric Catalysis with Hydrogen Chloride: Enantioselective Ring-Opening of Aziridines Catalyzed by a Phosphinothiourea.

    Science.gov (United States)

    Mita, Tsuyoshi; Jacobsen, Eric N

    2009-06-01

    Ring-opening of aziridines with hydrogen chloride to form β-chloroamine derivatives is catalyzed by a chiral phosphinothiourea derivative in high yields and with high enantioselectivities. On the basis of (31)P NMR studies, activation of HCl appears to proceed via quantitative protonation of the catalyst to afford a phosphonium chloride complex.

  8. Asymmetric transfer hydrogenation of imines catalyzed by a polymer-immobilized chiral catalyst.

    Science.gov (United States)

    Haraguchi, Naoki; Tsuru, Keiichi; Arakawa, Yukihiro; Itsuno, Shinichi

    2009-01-07

    The asymmetric transfer hydrogenation of imines was performed with the use of a polymer-immobilized chiral catalyst. The chiral catalyst, prepared from crosslinked polystyrene-immobilized chiral 1,2-diamine monosulfonamide, was effective in the asymmetric transfer hydrogenation of N-benzyl imines in CH(2)Cl(2) to give a chiral amine in high yield and good enantioselectivity. Furthermore, an amphiphilic polymeric catalyst prepared from crosslinked polystyrene containing sulfonated groups successfully catalyzed the asymmetric transfer hydrogenation of cyclic imines in water. Enantioenriched secondary amines with up to 94% ee were obtained by using a polymeric catalyst.

  9. Rh-Catalyzed Chemo- and Enantioselective Hydrogenation of Allylic Hydrazones.

    Science.gov (United States)

    Hu, Qiupeng; Hu, Yanhua; Liu, Yang; Zhang, Zhenfeng; Liu, Yangang; Zhang, Wanbin

    2017-01-23

    A highly efficient P-stereogenic diphosphine-rhodium complex was applied to the chemo- and enantioselective hydrogenation of allylic hydrazones for the synthesis of chiral allylic hydrazines in 89-96 % yields and with 82-99 % ee values. This methodology was successfully applied to the preparation of versatile chiral allylic amine derivatives.

  10. Selective Hydrogenation of Avermectin Catalyzed by Iridium-Phosphine Complexes

    Institute of Scientific and Technical Information of China (English)

    MA, Xiao-Yan; WANG, Kun; ZHANG, Lei; LI, Xian-Jun; LI, Rui-Xiang

    2007-01-01

    A series of new iridium complexes, IrCl(COD)(TMOPP) (1) [COD=1,5-cyclooctadiene, TMOPP=tris(4-methoxyphenyl)phosphine], IrCl(COD)(TFMPP) (2) [TFMPP = tris(4-trifluoromethylphenyl)phosphine], IrCl-(COD)(BDNA) (3) [BDNA=1,8-bis(diphenylphosphinomethyl)naphthalene], IrCl(COD)(BISBI) (4) [BISBI=2,2'-bis(diphenylphosphinomethyl)biphenyl] and IrCl(COD)(BDPB) (5) [BDPB = 1,2-bis(diphenylphosphinomethyl)benzene], were synthesized and characterized by NMR spectra and elemental analyses. In order to obtain the relationships between complex structures and their catalytic properties, IrCl(COD)(DPPM) (6) [DPPM=bis(diphenylphosphino)methane], IrCl(COD)(DPPE) (7) [DPPE= 1,2-bis(diphenylphosphino)ethane], IrCl(COD)-(DPPP) (8) [DPPP=1,3-bis(diphenylphosphino)propane] and IrCl(COD)(TPP) (9) [TPP=triphenylphosphine],were also synthesized according to the reported methods. The hydrogenation results showed that the low electronic density at the central metal was favorable to increase the catalytic activity for the hydrogenation of avermectin, but decrease the selectivity to ivermectin. The complex with a large chelating ring and a bulky chelating backbone would easily cause the cleavage of C-O bond in avermectin to give a byproduct avermectin aglycon.

  11. Immobilization of Chiral Ferrocenyl Ligands on Silica Gel and their Testing in Pd-catalyzed Allylic Substitution and Rh-catalyzed Hydrogenation

    Directory of Open Access Journals (Sweden)

    Duncan J. Macquarrie

    2005-07-01

    Full Text Available Five different silica gels containing two chiral ferrocenyl ligands were prepared by various synthetic routes and tested in an enantioselective Pd(0-catalyzed allylic substitution and Rh-catalyzed hydrogenation. All the prepared anchored ligands were characterized by porosimetry data, DRIFTS spectra, thermal data and AAS. The aim of the work was to compare the influence of the carrier, surface properties and immobilization strategy on the performance of the catalyst.

  12. 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.

  13. 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.

  14. 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.

  15. Iron-Catalyzed Regioselective Transfer Hydrogenative Couplings of Unactivated Aldehydes with Simple Alkenes.

    Science.gov (United States)

    Zheng, Yan-Long; Liu, Yan-Yao; Wu, Yi-Mei; Wang, Yin-Xia; Lin, Yu-Tong; Ye, Mengchun

    2016-05-17

    An FeBr3 -catalyzed reductive coupling of various aldehydes with alkenes that proceeds through a direct hydride transfer pathway has been developed. With (i) PrOH as the hydrogen donor under mild conditions, previously challenging coupling reactions of unactivated alkyl and aryl aldehydes with simple alkenes, such as styrene derivatives and α-olefins, proceeded smoothly to furnish a diverse range of functionalized alcohols with complete linear regioselectivity.

  16. Hydrogenation of Toluidines Catalyzed by Silica-supported Carboxymethylcellulose-platinum Complex

    Institute of Scientific and Technical Information of China (English)

    WANG Xin; YANG Ji-huo; HUANG Mei-yu; JIANG Ying-yan

    2004-01-01

    The hydrogenation of toluidines catalyzed by silica-supported carboxymethyl cellulose platinum complex forms methylcyclohexlamines in high yields, such as m-toluidine to 3-methylcyclohexylamine, o-toluidine to 2-methylcyclohexylamine, and p-toluidine to 4-methylcyclohexylamine in 97%, 96.7% and 98.2% yields,respectively, at 30 C and under atmospheric hydrogen pressure. The yields were remarkably affected by the Pt content in the complex, the kind of solvent and the reaction temperature. The catalyst was very stable and could be reused several times without remarkable change in the catalytic activity.

  17. Synthesis of Novel C2-Symmetrical Bidentate Phosphoramidite Ligands for Rh-catalyzed Asymmetric Hydrogenation of β-(Acylamino)acrylates

    Institute of Scientific and Technical Information of China (English)

    Qing Heng ZENG; Xiang Ping HU; Xin Miao LIANG; Zhuo ZHENG

    2006-01-01

    Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates, up to 89% ee with full conversions was obtained.

  18. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

    Science.gov (United States)

    Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A

    2016-04-13

    We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active β-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis.

  19. Development of photovoltaic hydrogen and hypochlorite generator

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, J.L.; Beltran, E.D.; Meas, Y.; Ortega, R.; Orozco, G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Mexico City (Mexico)

    2010-07-15

    Sodium hypochlorite is among the most efficient methods to disinfect water. Although sodium hypochlorite can be generated from chemical reactions of chlorine gas, the transportation of chlorine is a safety concern. In-situ generation of sodium hypochlorite in an electrolysis cell is therefore desirable. This study examined the feasibility of electrolytically producing both hypochlorite and hydrogen using photovoltaic energy. Since the hydrogen can be used in fuel cells to generate electricity and the hypochlorite can be used to purify drinking water, the integrated process may be operated economically because the products from both the anode and the cathode are valuable. The apparatus used in this study was designed and constructed in such a way that the photovoltaic module was coupled to the hydrogen and hypochlorite generator. The apparatus is suitable for operation in remote areas. The rates of hydrogen and hypochlorite generation were measured and the current/voltage characteristics of both the PV module and the electrolysis cell were analyzed. The electrolytic process yielded a sodium hypochlorite solution that was stable at pH 7. This study showed that environmental conditions such as solar intensity, ambient temperature and surface temperature of the photovoltaic module have a small effect on the rate of hydrogen production. Photovoltaic cells can supply the necessary electric current and voltage to produce 5 litres of 3.5 g/l NaOCl daily when a membrane is incorporated in the cell. The quantity of sodium hypochlorite produced by membraneless electrolysis with 2 photovoltaic modules could purify water for 40 families. It was concluded that long-term testing under real operating conditions is needed in order to estimate the capital cost of the equipment. 15 refs., 8 tabs., 5 figs.

  20. CO2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand.

    Science.gov (United States)

    Onishi, Naoya; Xu, Shaoan; Manaka, Yuichi; Suna, Yuki; Wang, Wan-Hui; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

    2015-06-01

    The catalytic cycle for the production of formic acid by CO2 hydrogenation and the reverse reaction have received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO2 hydrogenation catalyzed by iridium complexes bearing sophisticated N^N-bidentate ligands is reported. We describe how a ligand containing hydroxy groups as proton-responsive substituents enhances the catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interactions. In particular, [(Cp*IrCl)2(TH2BPM)]Cl2 (Cp* = pentamethylcyclopentadienyl; TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) enormously promotes the catalytic hydrogenation of CO2 in basic water by these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands were applied to CO2 hydrogenation. The catalytic efficiencies of the azole-type complexes were much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH2)]SO4. Furthermore, the introduction of one or more hydroxy groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxypyrimidine, and 4-pyrazolyl-2,6-dihydroxypyrimidine enhanced the catalytic activity. It is clear that the incorporation of additional electron-donating functionalities into proton-responsive azole-type ligands is effective for promoting further enhanced hydrogenation of CO2.

  1. 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.

  2. 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…

  3. 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.

  4. Alumina-entrapped Ag catalyzed nitro compounds coupled with alcohols using borrowing hydrogen methodology.

    Science.gov (United States)

    Liu, Huihui; Chuah, Gaik Khuan; Jaenicke, Stephan

    2015-06-14

    Supported silver catalysts were reported for the first time to be able to catalyze the coupling reaction between nitroarenes and alcohols via the borrowing hydrogen scheme. The recyclable, non-leaching catalyst is synthesized by the entrapment method, which allows entrapping of silver nanoparticles in an alumina matrix. Alcohols, acting as the reducing agents for nitro-groups, alkylated the resultant amines smoothly over these silver catalysts giving a yield of >98% towards the N-substituted amines. In this process, multiple steps were realized in one-pot over a single catalyst with very high efficiency. It offers another clean and economic way to achieve amination of alcohols.

  5. 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.

  6. 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...

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

    Directory of Open Access Journals (Sweden)

    Katsuaki Tanabe

    2016-01-01

    Full Text Available 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.

  8. 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.

  9. Hanford Waste Vitrification Plant hydrogen generation

    Energy Technology Data Exchange (ETDEWEB)

    King, R.B.; King, A.D. Jr.; Bhattacharyya, N.K. [and others

    1996-02-01

    The most promising method for the disposal of highly radioactive nuclear wastes is a vitrification process in which the wastes are incorporated into borosilicate glass logs, the logs are sealed into welded stainless steel canisters, and the canisters are buried in suitably protected burial sites for disposal. The purpose of the research supported by the Hanford Waste Vitrification Plant (HWVP) project of the Department of Energy through Battelle Pacific Northwest Laboratory (PNL) and summarized in this report was to gain a basic understanding of the hydrogen generation process and to predict the rate and amount of hydrogen generation during the treatment of HWVP feed simulants with formic acid. The objectives of the study were to determine the key feed components and process variables which enhance or inhibit the.production of hydrogen. Information on the kinetics and stoichiometry of relevant formic acid reactions were sought to provide a basis for viable mechanistic proposals. The chemical reactions were characterized through the production and consumption of the key gaseous products such as H{sub 2}. CO{sub 2}, N{sub 2}0, NO, and NH{sub 3}. For this mason this research program relied heavily on analyses of the gases produced and consumed during reactions of the HWVP feed simulants with formic acid under various conditions. Such analyses, used gas chromatographic equipment and expertise at the University of Georgia for the separation and determination of H{sub 2}, CO, CO{sub 2}, N{sub 2}, N{sub 2}O and NO.

  10. 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

  11. Rh-Catalyzed Asymmetric Hydrogenation of α-Substituted Vinyl Sulfones: An Efficient Approach to Chiral Sulfones.

    Science.gov (United States)

    Shi, Liyang; Wei, Biao; Yin, Xuguang; Xue, Peng; Lv, Hui; Zhang, Xumu

    2017-03-03

    Rh/(S)-(+)-DTBM-Segphos complex catalyzed asymmetric hydrogenation of α-substituted vinyl sulfones has been achieved, furnishing the desired products in high yields and excellent enantioselectivities (>90% yield, up to 99% ee). This method provided an efficient approach to α-substituted chiral sulfones under mild conditions and has potential applications in organic synthesis.

  12. Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems.

    Science.gov (United States)

    Zhang, Wei; Lai, Wenzhen; Cao, Rui

    2017-02-22

    Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.

  13. 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.

  14. 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

  15. Electroless Nickel-Based Catalyst for Diffusion Limited Hydrogen Generation through Hydrolysis of Borohydride

    Directory of Open Access Journals (Sweden)

    Shannon P. Anderson

    2013-07-01

    Full Text Available Catalysts based on electroless nickel and bi-metallic nickel-molybdenum nanoparticles were synthesized for the hydrolysis of sodium borohydride for hydrogen generation. The catalysts were synthesized by polymer-stabilized Pd nanoparticle-catalyzation and activation of Al2O3 substrate and electroless Ni or Ni-Mo plating of the substrate for selected time lengths. Catalytic activity of the synthesized catalysts was tested for the hydrolyzation of alkaline-stabilized NaBH4 solution for hydrogen generation. The effects of electroless plating time lengths, temperature and NaBH4 concentration on hydrogen generation rates were analyzed and discussed. Compositional analysis and surface morphology were carried out for nano-metallized Al2O3 using Scanning Electron Micrographs (SEM and Energy Dispersive X-Ray Microanalysis (EDAX. The as-plated polymer-stabilized electroless nickel catalyst plated for 10 min and unstirred in the hydrolysis reaction exhibited appreciable catalytic activity for hydrolysis of NaBH4. For a zero-order reaction assumption, activation energy of hydrogen generation using the catalyst was estimated at 104.6 kJ/mol. Suggestions are provided for further work needed prior to using the catalyst for portable hydrogen generation from aqueous alkaline-stabilized NaBH4 solution for fuel cells.

  16. Review of Catalytic Hydrogen Generation in the Defense Waste Processing Facility (DWPF) Chemical Processing Cell

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D. C.

    2004-12-31

    This report was prepared to fulfill the Phase I deliverable for HLW/DWPF/TTR-98-0018, Rev. 2, ''Hydrogen Generation in the DWPF Chemical Processing Cell'', 6/4/2001. The primary objective for the preliminary phase of the hydrogen generation study was to complete a review of past data on hydrogen generation and to prepare a summary of the findings. The understanding was that the focus should be on catalytic hydrogen generation, not on hydrogen generation by radiolysis. The secondary objective was to develop scope for follow-up experimental and analytical work. The majority of this report provides a summary of past hydrogen generation work with radioactive and simulated Savannah River Site (SRS) waste sludges. The report also includes some work done with Hanford waste sludges and simulants. The review extends to idealized systems containing no sludge, such as solutions of sodium formate and formic acid doped with a noble metal catalyst. This includes general information from the literature, as well as the focused study done by the University of Georgia for the SRS. The various studies had a number of points of universal agreement. For example, noble metals, such as Pd, Rh, and Ru, catalyze hydrogen generation from formic acid and formate ions, and more acid leads to more hydrogen generation. There were also some points of disagreement between different sources on a few topics such as the impact of mercury on the noble metal catalysts and the identity of the most active catalyst species. Finally, there were some issues of potential interest to SRS that apparently have not been systematically studied, e.g. the role of nitrite ion in catalyst activation and reactivity. The review includes studies covering the period from about 1924-2002, or from before the discovery of hydrogen generation during simulant sludge processing in 1988 through the Shielded Cells qualification testing for Sludge Batch 2. The review of prior studies is followed by a

  17. 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.

  18. Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

    Science.gov (United States)

    Zhang, Pan; Ni, Shao-Fei; Dang, Li

    2016-09-20

    The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation.

  19. 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

  20. Hydrogen generation from magnesium hydride by using organic acid

    Science.gov (United States)

    Ho, Yen-Hsi

    In this paper, the hydrolysis of solid magnesium hydride has been studied with the high concentration of catalyst at the varying temperature. An organic acid (acetic acid, CH3COOH) has been chosen as the catalyst. The study has three objectives: first, using three different weights of MgH 2 react with aqueous solution of acid for the hydrogen generation experiments. Secondly, utilizing acetic acid as the catalyst accelerates hydrogen generation. Third, emphasizing the combination of the three operating conditions (the weight of MgH2, the concentration of acetic acid, and the varying temperature) influence the amount of hydrogen generation. The experiments results show acetic acid truly can increase the rate of hydrogen generation and the weight of MgH2 can affect the amount of hydrogen generation more than the varying temperature.

  1. Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A.

    1999-07-14

    Supercritical carbon dioxide (scCO{sub 2}) was shown to be a reaction medium with unique properties for highly efficient iridium-catalyzed enantioselective hydrogenation of prochiral imines. Cationic iridium(I) complexes with chiral phosphinodihydrooxazoles, modified with perfluoroalkyl groups in the ligand or in the anion, were synthesized and tested in the hydrogenation of N-(1-phenylethylidene)aniline. Both the side chains and the lipophilic anions increased the solubility, but the choice of the anion also had a dramatic effect on the enantioselectivity with tetrakis-3,5-bis(trifluoromethyl)phenylborate (BARF) leading to the highest asymmetric induction. (R)-N-phenyl-1-phenylethylamine was formed quantitatively within 1 h in scCO{sub 2}[d(CO{sub 2}) = 0.75 g mL{sup {minus}1}] at 40 C and a H{sub 2} pressure of 30 bar with enantiomeric excesses of up to 81% using 0.078 mol % catalyst. The use of scCO{sub 2} instead of conventional solvents such as CH{sub 2}Cl{sub 2} allowed the catalyst loading to be lowered significantly owing to a change in the rate profile of the reaction. the homogeneous nature of the catalytically active species under the reaction conditions was demonstrated and was found to depend strongly on the composition of the reaction mixture and especially on the presence of the substrate. Utilizing the selective extractive properties of scCO{sub 2}, the product could be readily separated from the catalyst, which could be recycled several times without significant loss of activity and enantioselectivity. High-pressure FT-IR and NMR investigations revealed that the reactivity of the products to form the corresponding carbamic acids plays an important role for the application of this new methodology.

  2. 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.

  3. 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.

  4. 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.

  5. 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...

  6. 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...

  7. 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.

  8. Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

    Science.gov (United States)

    Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

    2010-05-25

    There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

  9. 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.

  10. 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.

  11. 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.

  12. Tandem amine and ruthenium-catalyzed hydrogenation of CO2 to methanol.

    Science.gov (United States)

    Rezayee, Nomaan M; Huff, Chelsea A; Sanford, Melanie S

    2015-01-28

    This Communication describes the hydrogenation of carbon dioxide to methanol via tandem catalysis with dimethylamine and a homogeneous ruthenium complex. Unlike previous examples with homogeneous catalysts, this CO2-to-CH3OH process proceeds under basic reaction conditions. The dimethylamine is proposed to play a dual role in this system. It reacts directly with CO2 to produce dimethylammonium dimethylcarbamate, and it also intercepts the intermediate formic acid to generate dimethylformamide. With the appropriate selection of catalyst and reaction conditions, >95% conversion of CO2 was achieved to form a mixture of CH3OH and dimethylformamide.

  13. 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

  14. Thermochemical hydrogen generation of indium oxide thin films

    Science.gov (United States)

    Lim, Taekyung; Ju, Sanghyun

    2017-03-01

    Development of alternative energy resources is an urgent requirement to alleviate current energy constraints. As such, hydrogen gas is gaining attention as a future alternative energy source to address existing issues related to limited energy resources and air pollution. In this study, hydrogen generation by a thermochemical water-splitting process using two types of In2O3 thin films was investigated. The two In2O3 thin films prepared by chemical vapor deposition (CVD) and sputtering deposition systems contained different numbers of oxygen vacancies, which were directly related to hydrogen generation. The as-grown In2O3 thin film prepared by CVD generated a large amount of hydrogen because of its abundant oxygen vacancies, while that prepared by sputtering had few oxygen vacancies, resulting in low hydrogen generation. Increasing the temperature of the In2O3 thin film in the reaction chamber caused an increase in hydrogen generation. The oxygen-vacancy-rich In2O3 thin film is expected to provide a highly effective production of hydrogen as a sustainable and efficient energy source.

  15. 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...

  16. 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.

  17. Cold weather hydrogen generation system and method of operation

    Science.gov (United States)

    Dreier, Ken Wayne; Kowalski, Michael Thomas; Porter, Stephen Charles; Chow, Oscar Ken; Borland, Nicholas Paul; Goyette, Stephen Arthur

    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.

  18. Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst

    Science.gov (United States)

    Chou, Chang-Chen; Chen, Bing-Hung

    2015-10-01

    Hydrogen generation from the catalyzed deliquescence/hydrolysis of ammonia borane (AB) using the Ni-Co catalyst supported on the graphene oxide (Ni-Co/r-GO catalyst) under the conditions of limited water supply was studied with the molar feed ratio of water to ammonia borane (denoted as H2O/AB) at 2.02, 3.97 and 5.93, respectively. The conversion efficiency of ammonia borane to hydrogen was estimated both from the cumulative volume of the hydrogen gas generated and the conversion of boron chemistry in the hydrolysates analyzed by the solid-state 11B NMR. The conversion efficiency of ammonia borane could reach nearly 100% under excess water dosage, that is, H2O/AB = 3.97 and 5.93. Notably, the hydrogen storage capacity could reach as high as 6.5 wt.% in the case with H2O/AB = 2.02. The hydrolysates of ammonia borane in the presence of Ni-Co/r-GO catalyst were mainly the mixture of boric acid and metaborate according to XRD, FT-IR and solid-state 11B NMR analyses.

  19. Apparatus for hydrogen and carbon production via carbon aerosol-catalyzed dissociation of hydrocarbons

    Science.gov (United States)

    Muradov, Nazim Z. (Inventor); Smith, Franklyn (Inventor); Tabatabaie-Raissi, Ali (Inventor)

    2012-01-01

    A novel process and apparatus is disclosed for sustainable, continuous production of hydrogen and carbon by catalytic dissociation or decomposition of hydrocarbons at elevated temperatures using in-situ generated carbon particles. Carbon particles are produced by decomposition of carbonaceous materials in response to an energy input. The energy input can be provided by at least one of a non-oxidative and oxidative means. The non-oxidative means of the energy input includes a high temperature source, or different types of plasma, such as, thermal, non-thermal, microwave, corona discharge, glow discharge, dielectric barrier discharge, or radiation sources, such as, electron beam, gamma, ultraviolet (UV). The oxidative means of the energy input includes oxygen, air, ozone, nitrous oxide (NO.sub.2) and other oxidizing agents. The method, apparatus and process of the present invention is applicable to any gaseous or liquid hydrocarbon fuel and it produces no or significantly less CO.sub.2 emissions compared to conventional processes.

  20. Direct observation and modelling of ordered hydrogen adsorption and catalyzed ortho-para conversion on ETS-10 titanosilicate material.

    Science.gov (United States)

    Ricchiardi, Gabriele; Vitillo, Jenny G; Cocina, Donato; Gribov, Evgueni N; Zecchina, Adriano

    2007-06-07

    Hydrogen physisorption on porous high surface materials is investigated for the purpose of hydrogen storage and hydrogen separation, because of its simplicity and intrinsic reversibility. For these purposes, the understanding of the binding of dihydrogen to materials, of the structure of the adsorbed phase and of the ortho-para conversion during thermal and pressure cycles are crucial for the development of new hydrogen adsorbents. We report the direct observation by IR spectroscopic methods of structured hydrogen adsorption on a porous titanosilicate (ETS-10), with resolution of the kinetics of the ortho-para transition, and an interpretation of the structure of the adsorbed phase based on classical atomistic simulations. Distinct infrared signals of o- and p-H2 in different adsorbed states are measured, and the conversion of o- to p-H2 is monitored over a timescale of hours, indicating the presence of a catalyzed reaction. Hydrogen adsorption occurs in three different regimes characterized by well separated IR manifestations: at low pressures ordered 1:1 adducts with Na and K ions exposed in the channels of the material are formed, which gradually convert into ordered 2:1 adducts. Further addition of H2 occurs only through the formation of a disordered condensed phase. The binding enthalpy of the Na+-H2 1:1 adduct is of -8.7+/-0.1 kJ mol(-1), as measured spectroscopically. Modeling of the weak interaction of H2 with the materials requires an accurate force field with a precise description of both dispersion and electrostatics. A novel three body force field for molecular hydrogen is presented, based on the fitting of an accurate PES for the H2-H2 interaction to the experimental dipole polarizability and quadrupole moment. Molecular mechanics simulations of hydrogen adsorption at different coverages confirm the three regimes of adsorption and the structure of the adsorbed phase.

  1. 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)

  2. 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.

  3. 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)

  4. 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.

  5. 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.

  6. 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.

  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. 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.

  9. Molecular cobalt pentapyridine catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Sun, Yujie

    2013-11-05

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition including the moiety of the general formula. [(PY5Me.sub.2)CoL].sup.2+, where L can be H.sub.2O, OH.sup.-, a halide, alcohol, ether, amine, and the like. In embodiments of the invention, water, such as tap water or sea water can be subject to low electric potentials, with the result being, among other things, the generation of hydrogen.

  10. 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

  11. Development of a low cost, portable solar hydrogen generation device

    Science.gov (United States)

    Rose, Kyle; Aggarwal, M. D.; Batra, Ashok; Wingo, Dennis

    2014-10-01

    Hydrogen is a clean energy source that is environmentally friendly and safe. It is well known that electrolysis is a common method used to produce hydrogen. Other high cost methods for hydrogen production can be countered by the development of this low cost pulse width modulated circuit, using direct current provided by naturally existing solar energy as a power source. Efforts are being made in the scientific community to produce a low cost, portable, solar hydrogen generating device for a number of clean energy applications such as fuel cells and energy storage. Proof of concept has already been tested in the laboratory and a small prototype system is being designed and fabricated in the workshop at Alabama A&M University. Our results of this study and details of the electronic circuit and the prototype are presented.

  12. Isoprene gas phase hydrogenation catalyzed by ThNi{sub 2} and UNi{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Branco, Joaquim Badalo [Departamento de Quimica, Instituto Tecnologico e Nuclear, Estrada Nacional 10, P-2686-953 Sacavem Codex (Portugal)], E-mail: jbranco@itn.pt; Goncalves, Antonio Pereira; Pires de Mato, Antonio [Departamento de Quimica, Instituto Tecnologico e Nuclear, Estrada Nacional 10, P-2686-953 Sacavem Codex (Portugal)

    2008-10-06

    The study of isoprene (2-methyl-1,3-butadiene) gas phase hydrogenation on ThNi{sub 2} and UNi{sub 2} was undertaken and the effect of the 5f element on nickel catalytic behavior investigated. At nearly steady state, the reaction products were isopentane and isopentenes (2-methyl-2-butene, 2-methyl-1-butene and 3-methyl-1-butene). The total selectivity to isopentenes was higher on ThNi{sub 2} ({approx}80 mol%) than on UNi{sub 2} ({approx}50 mol%) but, in both cases lower than that on pure Ni ({approx}96 mol%). The sum of 2-methyl-2-butene + 2-methyl-1-butene selectivities (valuable products for the tert-amyl methyl ether process) was {approx}75 mol% on ThNi{sub 2}, whereas on UNi{sub 2} it was significantly lower ({approx}50 mol%). ThNi{sub 2} and UNi{sub 2} total selectivity to isopentenes is nearly time invariant. The difference of catalytic properties between ThNi{sub 2} and UNi{sub 2} can be explained by electronic transfer from the 5f element to Ni that generates an electronic density supply on nickel, which is higher on ThNi{sub 2}.

  13. Insight into the electronic effect of phosphine ligand on Rh catalyzed CO2 hydrogenation by investigating the reaction mechanism.

    Science.gov (United States)

    Ni, Shao-Fei; Dang, Li

    2016-02-14

    Improving the catalytic efficiency of CO2 hydrogenation is a big challenge in catalysed CO2 recycling and H2 conservation. The detailed mechanism of [Rh(PCH2X(R)CH2P)2](+) (X(R) = CH2, N-CH3, CF2) catalyzed CO2 hydrogenation is studied to obtain insights into the electronic effect of the substituents at diphosphine ligand on the catalytic efficiency. The most favorable reaction mechanism is found to be composed of three steps: (1) oxidative addition of dihydrogen onto the Rh center of the catalyst; (2) the first hydride abstraction by base from the Rh dihydride complexes; (3) the second hydride transfer from the Rh hydride complexes to CO2. It was found that the transition state for the first hydride abstraction from the Rh dihydride complex is the TOF-determining transition state (TDTS) in the most favorable mechanism. The energetic span (δE) of the cycle is suggested related to the thermodynamic hydricity of the Rh dihydride complex. Model catalyst [Rh(PCH2CF2CH2P)2](+) with a strong σ electron withdrawing group on the diphosphine ligand provides higher hydricity in the Rh dihydride complex and lower activation energy when compared with the other two catalysts. Our study shows that it is the σ electron withdrawing ability rather than the electron donating ability that enhances the catalytic efficiency in catalyzed CO2 hydrogenation. This finding will benefit ligand design in transition metal catalysts and lead to more efficient methods for CO2 transformation.

  14. 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.

  15. 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.

  16. Efficiency of nuclear energy generation by hydrogen burning

    Energy Technology Data Exchange (ETDEWEB)

    Mitalas, R.

    1989-03-01

    An explicit formula for the efficiency of the PP chain energy generation in terms of the branching fractions to the three PP chains is derived and the variation of the efficiency with temperature and hydrogen abundance is illustrated. The PP chain efficiency is shown to have a minimum as a function of Y/X. The combined efficiency of simultaneous nuclear energy generation by the PP chain and the equilibrium CN cycle is then presented. 6 refs.

  17. A new paradigm for XOR-catalyzed reactive species generation in the endothelium.

    Science.gov (United States)

    Kelley, Eric E

    2015-08-01

    A plethora of vascular pathology is associated with inflammation, hypoxia and elevated rates of reactive species generation. A critical source of these reactive species is the purine catabolizing enzyme xanthine oxidoreductase (XOR) as numerous reports over the past 30 years have demonstrated XOR inhibition to be salutary. Despite this long standing association between increased vascular XOR activity and negative clinical outcomes, recent reports reveal a new paradigm whereby the enzymatic activity of XOR mediates beneficial outcomes by catalyzing the one electron reduction of nitrite (NO2(-)) to nitric oxide (NO) when NO2(-) and/or nitrate (NO3(-)) levels are enhanced either via dietary or pharmacologic means. These observations seemingly countervail numerous reports of improved outcomes in similar models upon XOR inhibition in the absence of NO2(-) treatment affirming the need for a more clear understanding of the mechanisms underpinning the product identity of XOR. To establish the micro-environmental conditions requisite for in vivo XOR-catalyzed oxidant and NO production, this review assesses the impact of pH, O2 tension, enzyme-endothelial interactions, substrate concentrations and catalytic differences between xanthine oxidase (XO) and xanthine dehydrogenase (XDH). As such, it reveals critical information necessary to distinguish if pursuit of NO2(-) supplementation will afford greater benefit than inhibition strategies and thus enhance the efficacy of current approaches to treat vascular pathology.

  18. A planar microfabricated electrolyzer for hydrogen and oxygen generation

    Science.gov (United States)

    Jiang, L.; Myer, B.; Tellefsen, K.; Pau, S.

    We present the design, fabrication and testing of a microfabricated planar reactor for the hydrogen evolution reaction (HER) using thin film Pt electrodes and polydimethylsiloxane (PDMS) fluidic chamber. The reactor is designed to separate gases by flow dynamics and reactor flow is analyzed by three-dimensional finite element analysis. The planar geometry is scalable, compact and stackable. Using KOH 28 wt% electrolyte, we have achieved a hydrogen generation density of 0.23 kg h -1 m -3 and an efficiency of 48% with a flow rate of 10 ml min -1 and cell voltage of 3 V.

  19. 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.

  20. Baeyer-Villiger oxidation of ketones with hydrogen peroxide catalyzed by Sn-aniline complex

    Institute of Scientific and Technical Information of China (English)

    Qing Hua Zhang; Shou Feng Wang; Zi Qiang Lei

    2007-01-01

    Sn-aniline complex was prepared by a simple procedure. Cyclic and acyclic ketones were oxidized into lactones or esters with very high selectivity and yield with 30% hydrogen peroxide in the presence of Sn-aniline complex.

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

    NARCIS (Netherlands)

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

    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

  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. 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.

  5. Autotrophic denitrification using hydrogen generated from metallic iron corrosion.

    Science.gov (United States)

    Sunger, Neha; Bose, Purnendu

    2009-09-01

    Hydrogenotrophic denitrification was demonstrated using hydrogen generated from anoxic corrosion of metallic iron. For this purpose, a mixture of hydrogenated water and nitrate solution was used as reactor feed. A semi-batch reactor with nitrate loading of 2000 mg m(-3) d(-1) and hydraulic retention time (HRT) of 50 days produced effluent with nitrate concentration of 0.27 mg N L(-1) (99% nitrate removal). A continuous flow reactor with nitrate loading of 28.9 mg m(-3) d(-1) and HRT of 15.6 days produced effluent with nitrate concentration of approximately 0.025 mg N L(-1) (95% nitrate removal). In both cases, the concentration of nitrate degradation by-products, viz., ammonia and nitrite, were below detection limits. The rate of denitrification in the reactors was controlled by hydrogen availability, and hence to operate such reactors at higher nitrate loading rates and/or lower HRT than reported in the present study, hydrogen concentration in the hydrogenated water must be significantly increased.

  6. 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.

  7. Hydrogen storage in Mg-LiBH4 composites catalyzed by FeF3

    Science.gov (United States)

    Puszkiel, Julián; Gennari, Fabiana C.; Arneodo Larochette, Pierre; Troiani, Horacio E.; Karimi, Fahim; Pistidda, Claudio; Gosalawit-Utke, Rapee; Jepsen, Julian; Jensen, Torben R.; Gundlach, Carsten; Tolkiehn, Martin; Bellosta von Colbe, José; Klassen, Thomas; Dornheim, Martin

    2014-12-01

    Mg-10 mol% LiBH4 composite plus small amounts of FeF3 is investigated in the present work. The presence of LiBH4 during the milling process noticeably modifies the size and morphology of the Mg agglomerates, leading to faster hydrogenation and reaching almost the theoretical hydrogen capacity owing to enhanced hydrogen diffusion mechanism. However, the dehydrogenation of the system at low temperatures (≤300 °C) is still slow. Thus, FeF3 addition is proposed to improve the dehydrogenation kinetic behavior. From experimental results, it is found that the presence of FeF3 results in an additional size reduction of the Mg agglomerates between ∼10 and ∼100 μm and the formation of stable phases such as MgF2, LiF and FeB. The FeB species might have a catalytic effect upon the MgH2 decomposition. As a further result of the FeF3 addition, the Mg-10 mol%LiBH4-5 mol% FeF3 material shows improved dehydrogenation properties: reduced dehydrogenation activation energy, faster hydrogen desorption rate and reversible hydrogen capacities of about 5 wt% at 275 °C.

  8. 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.

  9. 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.

  10. A molecular copper catalyst for electrochemical water reduction with a large hydrogen-generation rate constant in aqueous solution.

    Science.gov (United States)

    Zhang, Peili; Wang, Mei; Yang, Yong; Yao, Tianyi; Sun, Licheng

    2014-12-08

    The copper complex [(bztpen)Cu](BF4)2 (bztpen=N-benzyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine) displays high catalytic activity for electrochemical proton reduction in acidic aqueous solutions, with a calculated hydrogen-generation rate constant (k(obs)) of over 10000 s(-1). A turnover frequency (TOF) of 7000 h(-1) cm(-2) and a Faradaic efficiency of 96% were obtained from a controlled potential electrolysis (CPE) experiment with [(bztpen)Cu](2+) in pH 2.5 buffer solution at -0.90 V versus the standard hydrogen electrode (SHE) over two hours using a glassy carbon electrode. A mechanism involving two proton-coupled reduction steps was proposed for the dihydrogen generation reaction catalyzed by [(bztpen)Cu](2+).

  11. Pd/C synthesized with citric acid: an efficient catalyst for hydrogen generation from formic acid/sodium formate.

    Science.gov (United States)

    Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

    2012-01-01

    A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160 min and 64 mol H(2) mol(-1) catalyst h(-1), respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells.

  12. 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.

  13. High Selective Hydrogenation of Acetophenone Catalyzed by Alumina Supported Platinum Nanoclusters

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new preparation and reduction method of γ-Al2O3 supported and PVP stabilized platinum nanoclusters was studied.The catalyst exhibited very high activity and selectivity for acetophenone hydrogenation in isopropanol-KOH solution at 25~60°C and P H2=1~5 MPa.

  14. 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.

  15. 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.

  16. Optimized hydrogen generation in a semicontinuous sodium borohydride hydrolysis reactor for a 60 W-scale fuel cell stack

    Science.gov (United States)

    Arzac, G. M.; Fernández, A.; Justo, A.; Sarmiento, B.; Jiménez, M. A.; Jiménez, M. M.

    Catalyzed hydrolysis of sodium borohydride (SBH) is a promising method for the hydrogen supply of fuel cells. In this study a system for controlled production of hydrogen from aqueous sodium borohydride (SBH) solutions has been designed and built. This simple and low cost system operates under controlled addition of stabilized SBH solutions (fuel solutions) to a supported CoB catalyst. The system works at constant temperature delivering hydrogen at 1 L min -1 constant rate to match a 60-W polymer electrolyte membrane fuel cell (PEMFC). For optimization of the system, several experimental conditions were changed and their effect was investigated. A simple model based only on thermodynamic considerations was proposed to optimize system parameters at constant temperature and hydrogen evolution rate. It was found that, for a given SBH concentration, the use of the adequate fuel addition rate can maximize the total conversion and therefore the gravimetric storage capacity. The hydrogen storage capacity was as high as 3.5 wt% for 19 wt% SBH solution at 90% fuel conversion and an operation temperature of 60 °C. It has been demonstrated that these optimized values can also be achieved for a wide range of hydrogen generation rates. Studies on the durability of the catalyst showed that a regeneration step is needed to restore the catalytic activity before reusing.

  17. 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

  18. 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.

  19. Aluminum chloride for accelerating hydrogen generation from sodium borohydride

    Science.gov (United States)

    Demirci, U. B.; Akdim, O.; Miele, P.

    The present research paper reports preliminary results about the utilization of anhydrous aluminum chloride (AlCl 3) for accelerating hydrogen generation through hydrolysis of aqueous solution of sodium borohydride (NaBH 4) at 80 °C. To the best of our knowledge, AlCl 3 has never been considered for that reaction although many transition metal salts had already been assessed. AlCl 3 reactivity was compared to those of AlCl 3·6H 2O, AlF 3, CoCl 2, RuCl 3 and NiCl 2. With AlCl 3 and a NaBH 4 solution having a gravimetric hydrogen storage capacity (GHSC) of 2.9 wt.%, almost 100% hydrogen was generated in few seconds, i.e., with a hydrogen generation rate (HGR) of 354 L min -1 g -1(Al). This HGR is one of the highest rates ever reported. Higher HGRs were obtained by mixing AlCl 3 with CoCl2, RuCl 3 or NiCl 2. For example, the system RuCl 3:AlCl 3 (50:50 mass proportion) showed a HGR > 1000 L min -1 g -1(Ru:Al). The hydrolysis by-products (once dried) were identified (by XRD, IR and elemental analysis) as being Al(OH) 3, NaCl and Na 2B(OH) 4Cl and it was observed that even in situ formed Al(OH) 3 has catalytic abilities with HGRs of 5 L min -1 g -1(Al). All of these preliminary results are discussed, which concludes that AlCl 3 has a potential as accelerator for single-use NaBH 4-based storage system.

  20. 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.

  1. Molecular metal-Oxo catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Efficient C2-Symmetric Chiral Schiff Bases for Lanthanide-catalyzed Asymmetric Hydrogenation of Acetophenone

    Institute of Scientific and Technical Information of China (English)

    Peng Fei YAN; Wen Bin SUN; Guang Ming LI; Chun Hong NIE; Zheng Yu YUE

    2006-01-01

    An array of C2-symmetric chiral Schiff bases of substituted salicylaldehyde (1R, 2R)-1,2-cyclohexanediamine and (R)-(+)-2, 2'-diamino-1, 1'-binaphthalene, incorporated with lanthanide complexes, have been applied as catalysts for asymmetric hydrogenation of acetophenone for the first time. Highly enantioselective product with 90% enantiomeric excess (e.e.) was obtained when the catalyst, hybridized by the bulky electron-donating 3, 5-di-tert-butyl substituted Schiff base (2) and SmCl3·4THF, was employed.

  7. Enhanced hydrogen sorption properties of Ni and Co-catalyzed MgH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Jianfeng [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Guo, Zaiping [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); School of Mechanical, Materials and Mechatronics Engineering, University of Wollongong, NSW 2522 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Yu, Xuebin [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Department of Materials Science, Fudan University, Shanghai 200433 (China); Liu, Huakun [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Wu, Zhu; Ni, Jun [Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)

    2010-05-15

    MgH{sub 2} is one of the most promising hydrogen storage materials due to its high capacity and low cost. In an effort to develop MgH{sub 2} with a low dehydriding temperature and fast sorption kinetics, doping MgH{sub 2} with NiCl{sub 2} and CoCl{sub 2} has been investigated in this paper. Both the dehydrogenation temperature and the absorption/desorption kinetics have been improved by adding either NiCl{sub 2} or CoCl{sub 2}, and a significant enhancement was obtained in the case of the NiCl{sub 2} doped sample. For example, a hydrogen absorption capacity of 5.17 wt% was reached at 300 C in 60 s for the MgH{sub 2}/NiCl{sub 2} sample. In contrast, the ball-milled MgH{sub 2} just absorbed 3.51 wt% hydrogen at 300 C in 400 s. An activation energy of 102.6 kJ/mol for the MgH{sub 2}/NiCl{sub 2} sample has been obtained from the desorption data, 18.7 kJ/mol and 55.9 kJ/mol smaller than those of the MgH{sub 2}/CoCl{sub 2}, which also exhibits an enhanced kinetics, and of the pure MgH{sub 2} sample, respectively. In addition, the enhanced kinetics was observed to persist even after 9 cycles in the case of the NiCl{sub 2} doped MgH{sub 2} sample. Further kinetic investigation indicated that the hydrogen desorption from the milled MgH{sub 2} is controlled by a slow, random nucleation and growth process, which is transformed into two-dimensional growth after NiCl{sub 2} or CoCl{sub 2} doping, suggesting that the additives reduced the barrier and lowered the driving forces for nucleation. (author)

  8. 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.

  9. 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.

  10. Cas9-catalyzed DNA Cleavage Generates Staggered Ends: Evidence from Molecular Dynamics Simulations

    Science.gov (United States)

    Zuo, Zhicheng; Liu, Jin

    2016-11-01

    The CRISPR-associated endonuclease Cas9 from Streptococcus pyogenes (spCas9) along with a single guide RNA (sgRNA) has emerged as a versatile toolbox for genome editing. Despite recent advances in the mechanism studies on spCas9-sgRNA-mediated double-stranded DNA (dsDNA) recognition and cleavage, it is still unclear how the catalytic Mg2+ ions induce the conformation changes toward the catalytic active state. It also remains controversial whether Cas9 generates blunt-ended or staggered-ended breaks with overhangs in the DNA. To investigate these issues, here we performed the first all-atom molecular dynamics simulations of the spCas9-sgRNA-dsDNA system with and without Mg2+ bound. The simulation results showed that binding of two Mg2+ ions at the RuvC domain active site could lead to structurally and energetically favorable coordination ready for the non-target DNA strand cleavage. Importantly, we demonstrated with our simulations that Cas9-catalyzed DNA cleavage produces 1-bp staggered ends rather than generally assumed blunt ends.

  11. Xanthine oxidoreductase-catalyzed reactive species generation: A process in critical need of reevaluation.

    Science.gov (United States)

    Cantu-Medellin, Nadiezhda; Kelley, Eric E

    2013-06-10

    Nearly 30 years have passed since the discovery of xanthine oxidoreductase (XOR) as a critical source of reactive species in ischemia/reperfusion injury. Since then, numerous inflammatory disease processes have been associated with elevated XOR activity and allied reactive species formation solidifying the ideology that enhancement of XOR activity equates to negative clinical outcomes. However, recent evidence may shatter this paradigm by describing a nitrate/nitrite reductase capacity for XOR whereby XOR may be considered a crucial source of beneficial (•)NO under ischemic/hypoxic/acidic conditions; settings similar to those that limit the functional capacity of nitric oxide synthase. Herein, we review XOR-catalyzed reactive species generation and identify key microenvironmental factors whose interplay impacts the identity of the reactive species (oxidants vs. (•)NO) produced. In doing so, we redefine existing dogma and shed new light on an enzyme that has weathered the evolutionary process not as gadfly but a crucial component in the maintenance of homeostasis.

  12. A Renewably Powered Hydrogen Generation and Fueling Station Community Project

    Science.gov (United States)

    Lyons, Valerie J.; Sekura, Linda S.; Prokopius, Paul; Theirl, Susan

    2009-01-01

    The proposed project goal is to encourage the use of renewable energy and clean fuel technologies for transportation and other applications while generating economic development. This can be done by creating an incubator for collaborators, and creating a manufacturing hub for the energy economy of the future by training both white- and blue-collar workers for the new energy economy. Hydrogen electrolyzer fueling stations could be mass-produced, shipped and installed in collaboration with renewable energy power stations, or installed connected to the grid with renewable power added later.

  13. Epoxidation of 1-Octene with hydrogen peroxide aqueous catalyzed by titania supported sulfonated coal

    Science.gov (United States)

    Nurhadi, Mukhamad

    2017-02-01

    Titania supported sulfonated coal was created as heterogeneous catalyst for epoxidation of 1-octene with aqueous hydrogen peroxide as oxidant at room temperature. The catalysts were prepared from coal that was sulfonated with H2SO4 (97%) and impregnated 7.2%wt with titanium(IV) isopropoxide (Ti(PrO)4). All catalysts coal (C), CS, Ti(7.2)-CS and Ti(7.2)-CSC were characterized by FTIR. The catalytic performance was tested for epoxidation of 1-octene with H2O2 aqueous as oxidant. It is found that Ti(7.2)-CS possessed the best catalytic performance and it gave the highest 1,2 epoxyoctene 322 µmol.

  14. 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.

  15. 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.

  16. DFT Methods to Study the Reaction Mechanism of Iridium-Catalyzed Hydrogenation of Olefins: Which Functional Should be Chosen?

    Science.gov (United States)

    Sun, Yihua; Chen, Hui

    2016-01-04

    To enable the selection of more accurate computational methods for the future theoretical exploration of the reaction mechanism of Ir-catalyzed olefin hydrogenation, we compared high-level ab initio coupled cluster and DFT calculations with a simplified model of Pfaltz's Ir/P,N-type catalyst for all four previously proposed Ir(I) /Ir(III) and Ir(III) /Ir(V) mechanisms. Through the systematic assessment of the DFT performances, the DFT empirical dispersion correction (DFT-D3) is found to be indispensable for improving the accuracy of relative energies between the Ir(I) /Ir(III) and Ir(III) /Ir(V) mechanisms. After including the DFT-D3 correction, the three best performing density functionals (DFs) are B2-PLYP, BP86, and TPSSh. In these recommended DFs, the computationally more expensive double-hybrid functional B2-PLYP-D3 has a balanced and outstanding performance for calculations of the reaction barriers, reaction energies, and energy gaps between different mechanisms, whereas the less costly BP86-D3 and TPSSh-D3 methods have outstanding, but relatively less uniform performances.

  17. 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.

  18. Amine-free reversible hydrogen storage in formate salts catalyzed by ruthenium pincer complex without pH control or solvent change.

    Science.gov (United States)

    Kothandaraman, Jotheeswari; Czaun, Miklos; Goeppert, Alain; Haiges, Ralf; Jones, John-Paul; May, Robert B; Prakash, G K Surya; Olah, George A

    2015-04-24

    Due to the intermittent nature of most renewable energy sources, such as solar and wind, energy storage is increasingly required. Since electricity is difficult to store, hydrogen obtained by electrochemical water splitting has been proposed as an energy carrier. However, the handling and transportation of hydrogen in large quantities is in itself a challenge. We therefore present here a method for hydrogen storage based on a CO2 (HCO3 (-) )/H2 and formate equilibrium. This amine-free and efficient reversible system (>90 % yield in both directions) is catalyzed by well-defined and commercially available Ru pincer complexes. The formate dehydrogenation was triggered by simple pressure swing without requiring external pH control or the change of either the solvent or the catalyst. Up to six hydrogenation-dehydrogenation cycles were performed and the catalyst performance remained steady with high selectivity (CO free H2 /CO2 mixture was produced).

  19. Oxidation of alcohols by hydrogen peroxide, catalyzed by methyltrioxorhenium (MTO): A hydride abstraction

    Energy Technology Data Exchange (ETDEWEB)

    Zauche, T.H.; Espenson, J.H. [Ames Lab., IA (United States)]|[Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

    1998-12-28

    Primary and secondary alcohols are oxidized using hydrogen peroxide as an oxygen donor and methyltrioxorhenium (MTO) as a catalyst. The methylrhenium di-peroxide, CH{sub 3}Re(O)({eta}{sub 2}-O{sub 2}){sub 2}(H{sub 2}O), was the dominant and reactive form of the catalyst. Representative rate constants k/L/mol s are 1.02 {times} 10{sup {minus}4} for 4-Me-{alpha}-methylbenzyl alcohol and 4.9 {times} 10{sup {minus}5} for 4-Cl-{alpha}-methylbenzyl alcohol. There was a kinetic isotope effect of 3.2 for the {alpha} C-H bond. When sec-phenethyl alcohol was labeled with {sup 18}O, 80% of the oxygen was retained in the ketone. Tests for the possible intervention of a free radical intermediate were carried out; the evidence was entirely negative. A mechanism featuring hydride abstraction is proposed, the first time for the H{sub 2}O{sub 2}/MTO system. Also, a cocatalytic set of reaction conditions has been developed on the synthetic scale, using bromide and MTO as cocatalysts, which cuts the reaction time from hours to minutes.

  20. 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.

  1. An integrated MEMS infrastructure for fuel processing: hydrogen generation and separation for portable power generation

    Science.gov (United States)

    Varady, M. J.; McLeod, L.; Meacham, J. M.; Degertekin, F. L.; Fedorov, A. G.

    2007-09-01

    Portable fuel cells are an enabling technology for high efficiency and ultra-high density distributed power generation, which is essential for many terrestrial and aerospace applications. A key element of fuel cell power sources is the fuel processor, which should have the capability to efficiently reform liquid fuels and produce high purity hydrogen that is consumed by the fuel cells. To this end, we are reporting on the development of two novel MEMS hydrogen generators with improved functionality achieved through an innovative process organization and system integration approach that exploits the advantages of transport and catalysis on the micro/nano scale. One fuel processor design utilizes transient, reverse-flow operation of an autothermal MEMS microreactor with an intimately integrated, micromachined ultrasonic fuel atomizer and a Pd/Ag membrane for in situ hydrogen separation from the product stream. The other design features a simpler, more compact planar structure with the atomized fuel ejected directly onto the catalyst layer, which is coupled to an integrated hydrogen selective membrane.

  2. 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.

  3. Enhanced photocatalytic hydrogen generation from barium tantalate composites.

    Science.gov (United States)

    Marschall, Roland; Soldat, Julia; Busser, G Wilma; Wark, Michael

    2013-04-01

    (111)-layered Ba5Ta4O15 photocatalysts were synthesised by a solid state reaction route and a citrate synthesis route, and their structural and electronic properties were investigated. After citrate route preparation, the presence of a second phase, namely Ba3Ta5O15, was determined by X-ray powder diffraction and absorption spectroscopy. The existence of this phase had a profound effect on the photocatalytic activity of this Ba5Ta4O15/Ba3Ta5O15 composite in comparison to the pure Ba5Ta4O15 materials. The photocatalytic performance of the barium tantalates was evaluated by investigating the capability in ˙OH radical formation and hydrogen generation. Strongly increased hydrogen evolution rates for the Ba5Ta4O15/Ba3Ta5O15 composite, up to 160% higher than for the pure Ba5Ta4O15, were determined, and only very small amounts of Rh co-catalyst, deposited on the photocatalysts by stepwise reductive photo-deposition, were needed to achieve these results.

  4. 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.

  5. A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Lyubimov, Artem Y. [Department of Molecular, Cell and Developmental Biology, University of California, Santa Cruz, Sinsheimer Laboratories, 1156 High Street, Santa Cruz, CA 95064 (United States); Chen, Lin; Sampson, Nicole S. [Department of Chemistry, Stony Brook University, Stony Brook, NY 11794-3400 (United States); Vrielink, Alice, E-mail: alice.vrielink@uwa.edu.au [School of Biomedical, Biomolecular and Chemical Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009 (Australia); Department of Molecular, Cell and Developmental Biology, University of California, Santa Cruz, Sinsheimer Laboratories, 1156 High Street, Santa Cruz, CA 95064 (United States)

    2009-11-01

    The importance of active-site electrostatics for oxidative and reductive half-reactions in a redox flavoenzyme (cholesterol oxidase) have been investigated by a combination of biochemistry and atomic resolution crystallography. A detailed examination of active-site dynamics demonstrates that the oxidation of substrate and the re-oxidation of the flavin cofactor by molecular oxygen are linked by a single active-site asparagine. Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3β-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH⋯π interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k{sub cat}. Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0 Å resolution) reveals significant perturbations in the active site. As predicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH⋯π interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered.

  6. 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.

  7. 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...

  8. 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.

  9. Systems and methods for generation of hydrogen peroxide vapor

    Science.gov (United States)

    Love, Adam H; Eckels, Joel Del; Vu, Alexander K; Alcaraz, Armando; Reynolds, John G

    2014-12-02

    A system according to one embodiment includes a moisture trap for drying air; at least one of a first container and a second container; and a mechanism for at least one of: bubbling dried air from the moisture trap through a hydrogen peroxide solution in the first container for producing a hydrogen peroxide vapor, and passing dried air from the moisture trap into a headspace above a hydrogen peroxide solution in the second container for producing a hydrogen peroxide vapor. A method according one embodiment includes at least one of bubbling dried air through a hydrogen peroxide solution in a container for producing a first hydrogen peroxide vapor, and passing dried air from the moisture trap into a headspace above the hydrogen peroxide solution in a container for producing a second hydrogen peroxide vapor. Additional systems and methods are also presented.

  10. 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

  11. Computational design of materials for solar hydrogen generation

    Science.gov (United States)

    Umezawa, Naoto

    Photocatalysis has a great potential for the production of hydrogen from aquerous solution under solar light. In this talk, two different approaches toward the computational materials desing for solar hydrogen generation will be presented. Tin (Sn), which has two major oxidation states, Sn2+ and Sn4+, is abundant on the earth's crust. Recently, visible-light responsive photocatalytc H2 evolution reaction was identified over a mixed valence tin oxide Sn3O4. We have carried out crystal structure prediction for mixed valence tin oxides in different atomic compositions under ambient pressure condition using advanced computational methods based on the evolutionary crystal-structure search and density-functional theory. The predicted novel crystal structures realize the desirable band gaps and band edge positions for H2 evolution under visible light irradiation. It is concluded that multivalent tin oxides have a great potential as an abundant, cheap and environmentally-benign solar-energy conversion photofunctional materials. Transition metal doping is effective for sensitizing SrTiO3 under visible light. We have theoretically investigated the roles of the doped Cr in STO based on hybrid density-functional calculations. Cr atoms are preferably substituting for Ti under any equilibrium growth conditions. The lower oxidation state Cr3+, which is stabilized under an n-type condition of STO, is found to be advantageous for the photocatalytic performance. It is firther predicted that lanthanum is the best codopant for stabilizing the favorable oxidation state, Cr3+. The prediction was validated by our experiments that La and Cr co-doped STO shows the best performance among examined samples. This work was supported by the Japan Science and Technology Agency (JST) Precursory Research for Embryonic Science and Technology (PRESTO) and International Research Fellow program of Japan Society for the Promotion of Science (JSPS) through project P14207.

  12. Visible and Near‐Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5

    Science.gov (United States)

    Jia, Jia; O'Brien, Paul G.; He, Le; Qiao, Qiao; Fei, Teng; Reyes, Laura M.; Burrow, Timothy E.; Dong, Yuchan; Liao, Kristine; Varela, Maria; Pennycook, Stephen J.; Hmadeh, Mohamad; Helmy, Amr S.; Kherani, Nazir P.; Perovic, Doug D.

    2016-01-01

    The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod‐supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat−1 h−1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas‐phase CO2 to valuable chemicals and fuels. PMID:27840802

  13. 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.

  14. Durable pd-based alloy and hydrogen generation membrane thereof

    Science.gov (United States)

    Benn, Raymond C.; Opalka, Susanne M.; Vanderspurt, Thomas Henry

    2010-02-02

    A durable Pd-based alloy is used for a H.sub.2-selective membrane in a hydrogen generator, as in the fuel processor of a fuel cell plant. The Pd-based alloy includes Cu as a binary element, and further includes "X", where "X" comprises at least one metal from group "M" that is BCC and acts to stabilize the .beta. BCC phase for stability during operating temperatures. The metal from group "M" is selected from the group consisting of Fe, Cr, Nb, Ta, V, Mo, and W, with Nb and Ta being most preferred. "X" may further comprise at least one metal from a group "N" that is non-BCC, preferably FCC, that enhances other properties of the membrane, such as ductility. The metal from group "N" is selected from the group consisting of Ag, Au, Re, Ru, Rh, Y, Ce, Ni, Ir, Pt, Co, La and In. The at. % of Pd in the binary Pd--Cu alloy ranges from about 35 at. % to about 55 at. %, and the at. % of "X" in the higher order alloy, based on said binary alloy, is in the range of about 1 at. % to about 15 at. %. The metals are selected according to a novel process.

  15. 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.

  16. Hydrogen generation by the hydrolysis reaction of ball-milled aluminium-lithium alloys

    Science.gov (United States)

    Chen, Xingyu; Zhao, Zhongwei; Liu, Xuheng; Hao, Mingming; Chen, Ailiang; Tang, Zhongyang

    2014-05-01

    The addition of Li can prevent an inert alumina film from forming on the surface of Al alloy particles, allowing the rapid hydrogen generation of Al alloys to be achieved. However, because the Li content is less than 10%, the hydrogen generation rate and hydrogen yield of Al-Li alloys are significantly decreased. In this work, NaCl is introduced to prepare Al-Li alloys with low Li contents by ball milling. The research results show that by increasing the amount of NaCl added, the ball milling time and Li content can effectively improve the hydrogen generation of the alloys. Under optimal preparation conditions, the ultimate hydrogen yield of Al-Li alloys can reach 100%. The initial water temperature has almost no effect on the generation of hydrogen, even at 0 °C. Ca2+ and Mg2+ can combine with OH- to form the insoluble compounds Ca(OH)2 and Mg(OH)2, which can prevent hydrogen generation. NO3- reacts with Al to form ammonia and reduce the hydrogen yield of the alloys. Therefore, Al-Li alloys should be prevented from reacting with water containing Ca2+, Mg2+ and NO3-. Al-Li alloys must be stored in isolation from air to maintain good hydrogen-generation performances.

  17. Electroless Plated Co-Ni-P-B/Ni Foam Catalyst for Hydrogen Generation from Sodium Borohydride.

    Science.gov (United States)

    Park, Daeil; Kim, Taegyu

    2016-02-01

    Co-Ni-P-B catalyst supported on Ni foam was prepared using electroless plating for hydrogen generation from an alkaline NaBH4 solution. Co-B, Co-P-B, and Co-Ni-B were prepared for comparison. Surface morphology of catalyst/Ni foams were observed using SEM analysis. The Co- Ni-P-B/Ni foam catalyst showed the superior performance on hydrogen generation rate due to the uniform formation of catalyst particles on the surface of Ni foam. Characteristics of hydrogen generation rate on the Co-N-P-B/Ni foam catalyst were investigated at the variety of NaBH4 and NaOH concentrations. The hydrogen generation rate increased with decreasing NaBH4 concentration, while increasing NaOH concentration. Durability test was performed, resulting in the stable hydrogen generation for 6 hours.

  18. 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.

  19. Commercializing larger PEM-based hydrogen generators for energy and industrial applications

    Energy Technology Data Exchange (ETDEWEB)

    Moulthrop, L.; Anderson, E.; Chow, O.; Friedland, R.; Porter, S. [Distributed Energy Systems, Wallingford, CT (United States)

    2007-07-01

    As economic, security and environmental drivers converge, there is a demand for larger and better on-site hydrogen generators. This paper outlined the measures needed to scale-up a commercial 12 kg/day proton exchange membrane (PEM) hydrogen generator to a 100 to 500 kg hydrogen per day capacity range. The commercial hydrogen generators using PEM water electrolysis are well proven and currently serve industrial applications worldwide in more than 50 countries. However, North American liquid hydrogen shortages, increasing trucking costs, developing economies with no liquid infrastructure, utilities, and forklift fuel cell fueling applications are all working to increase market demand for commercial on-site hydrogen generation. Water electrolysis was recently identified as the hydrogen technology that will enable solar renewable energy to fill the 17 TW carbon free energy gap projected worldwide by 2050. The scale-up must consider fixed cost as well as operating costs of the electrolyzer and power conditioning, compression and storage ancillaries. It was noted that although commercial applications may be well-satisfied with a 100 kg hydrogen/day PEM hydrogen generator module for the next five years, after that, the 500 kg hydrogen/day module will be required for hydrogen vehicle fueling stations, utility load-leveling, and renewables to hydrogen generation. It was suggested that a paced development effort can be synchronized with evolving fuel cell markets and market price points. The projection of future market price points can be generated using market data and specific cases of the H2A model developed by the United States Department of Energy for electrolysis based fueling. H2A modeling and system analysis identify the components and subsystem development priorities, requirements, and challenges. Codes and standards are maturing to help manufacturers and certification authorities make safe and compliant equipment. It was noted that this development effort is

  20. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    DEFF Research Database (Denmark)

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

    2015-01-01

    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......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...... 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...

  1. 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.

  2. 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.

  3. 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.

  4. Study on the Hydrogen Generation Rules of Coal Oxidation at Low Temperature

    Directory of Open Access Journals (Sweden)

    Shao He

    2014-07-01

    Full Text Available Based on a hydrogen desorption experiment and a comparative experiment of low-temperature coal oxidation performed prior to and after hydrogen desorption, this paper demonstrates the occurrence of hydrogen adsorption in coal at room temperature and reveals that the hydrogen generated in the process of coal oxidation originates from coal oxidation and desorption. The results show that the hydrogen accumulation generated only by coal oxidation and the hydrogen accumulation generated solely by desorption both exhibit a LangmuirEXT1 function equation relationship with temperature. The result of the present research can provide a theoretical basis for the accurate prediction of spontaneous coal combustion and is of great significance to the prevention and control of coal spontaneous combustion in coal mines, industrial coal storage and transportation.

  5. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

    Science.gov (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

    2017-03-08

    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines were evaluated.

  6. Free tyrosine and tyrosine-rich peptide-dependent superoxide generation catalyzed by a copper-binding, threonine-rich neurotoxic peptide derived from prion protein

    Directory of Open Access Journals (Sweden)

    Ken Yokawa, Tomoko Kagenishi, Kaishi Goto, Tomonori Kawano

    2009-01-01

    Full Text Available Previously, generation of superoxide anion (O2•- catalyzed by Cu-binding peptides derived from human prion protein (model sequence for helical Cu-binding motif VNITKQHTVTTTT was most active in the presence of catecholamines and related aromatic monoamines such as phenylethylamine and tyramine, has been reported [Kawano, T., Int J Biol Sci 2007; 3: 57-63]. The peptide sequence (corresponding to helix 2 tested here is known as threonine-rich neurotoxic peptide. In the present article, the redox behaviors of aromatic monoamines, 20 amino acids and prion-derived tyrosine-rich peptide sequences were compared as putative targets of the oxidative reactions mediated with the threonine-rich prion-peptide. For detection of O2•-, an O2•--specific chemiluminescence probe, Cypridina luciferin analog was used. We found that an aromatic amino acid, tyrosine (structurally similar to tyramine behaves as one of the best substrates for the O2•- generating reaction (conversion from hydrogen peroxide catalyzed by Cu-bound prion helical peptide. Data suggested that phenolic moiety is required to be an active substrate while the presence of neither carboxyl group nor amino group was necessarily required. In addition to the action of free tyrosine, effect of two tyrosine-rich peptide sequences YYR and DYEDRYYRENMHR found in human prion corresponding to the tyrosine-rich region was tested as putative substrates for the threonine-rich neurotoxic peptide. YYR motif (found twice in the Y-rich region showed 2- to 3-fold higher activity compared to free tyrosine. Comparison of Y-rich sequence consisted of 13 amino acids and its Y-to-F substitution mutant sequence revealed that the tyrosine-residues on Y-rich peptide derived from prion may contribute to the higher production of O2•-. These data suggest that the tyrosine residues on prion molecules could be additional targets of the prion-mediated reactions through intra- or inter-molecular interactions. Lastly

  7. Free tyrosine and tyrosine-rich peptide-dependent superoxide generation catalyzed by a copper-binding, threonine-rich neurotoxic peptide derived from prion protein.

    Science.gov (United States)

    Yokawa, Ken; Kagenishi, Tomoko; Goto, Kaishi; Kawano, Tomonori

    2009-01-01

    Previously, generation of superoxide anion (O(2)(*-)) catalyzed by Cu-binding peptides derived from human prion protein (model sequence for helical Cu-binding motif VNITKQHTVTTTT was most active) in the presence of catecholamines and related aromatic monoamines such as phenylethylamine and tyramine, has been reported [Kawano, T., Int J Biol Sci 2007; 3: 57-63]. The peptide sequence (corresponding to helix 2) tested here is known as threonine-rich neurotoxic peptide. In the present article, the redox behaviors of aromatic monoamines, 20 amino acids and prion-derived tyrosine-rich peptide sequences were compared as putative targets of the oxidative reactions mediated with the threonine-rich prion-peptide. For detection of O(2)(*-), an O(2)(*-)-specific chemiluminescence probe, Cypridina luciferin analog was used. We found that an aromatic amino acid, tyrosine (structurally similar to tyramine) behaves as one of the best substrates for the O(2)(*-) generating reaction (conversion from hydrogen peroxide) catalyzed by Cu-bound prion helical peptide. Data suggested that phenolic moiety is required to be an active substrate while the presence of neither carboxyl group nor amino group was necessarily required. In addition to the action of free tyrosine, effect of two tyrosine-rich peptide sequences YYR and DYEDRYYRENMHR found in human prion corresponding to the tyrosine-rich region was tested as putative substrates for the threonine-rich neurotoxic peptide. YYR motif (found twice in the Y-rich region) showed 2- to 3-fold higher activity compared to free tyrosine. Comparison of Y-rich sequence consisted of 13 amino acids and its Y-to-F substitution mutant sequence revealed that the tyrosine-residues on Y-rich peptide derived from prion may contribute to the higher production of O(2)(*-). These data suggest that the tyrosine residues on prion molecules could be additional targets of the prion-mediated reactions through intra- or inter-molecular interactions. Lastly, possible

  8. 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.

  9. 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...

  10. 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...

  11. 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.

  12. 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.

  13. 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.

  14. Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

    Science.gov (United States)

    Rhodes, Christopher P. (Inventor); Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Anderson, Kelvin C. (Inventor)

    2011-01-01

    A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

  15. 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.

  16. 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.

  17. Toxicological analysis of 17 autopsy cases of hydrogen sulfide poisoning resulting from the inhalation of intentionally generated hydrogen sulfide gas.

    Science.gov (United States)

    Maebashi, Kyoko; Iwadate, Kimiharu; Sakai, Kentaro; Takatsu, Akihiro; Fukui, Kenji; Aoyagi, Miwako; Ochiai, Eriko; Nagai, Tomonori

    2011-04-15

    Although many cases of fatal hydrogen sulfide poisoning have been reported, in most of these cases, it resulted from the accidental inhalation of hydrogen sulfide gas. In recent years, we experienced 17 autopsy cases of fatal hydrogen sulfide poisoning due to the inhalation of intentionally generated hydrogen sulfide gas. In this study, the concentrations of sulfide and thiosulfate in blood, urine, cerebrospinal fluid and pleural effusion were examined using GC/MS. The sulfide concentrations were blood: 0.11-31.84, urine: 0.01-1.28, cerebrospinal fluid: 0.02-1.59 and pleural effusion: 2.00-8.59 (μg/ml), while the thiosulfate concentrations were blood: 0-0.648, urine: 0-2.669, cerebrospinal fluid: 0.004-0.314 and pleural effusion: 0.019-0.140 (μmol/ml). In previous reports, the blood concentration of thiosulfate was said to be higher than that of sulfide in hydrogen sulfide poisoning cases, although the latter was higher than the former in 8 of the 14 cases examined in this study. These results are believed to be strongly influenced by the atmospheric concentration of hydrogen sulfide the victims were exposed to and the time interval between exposure and death.

  18. Autothermal hydrogen generation from methanol in a ceramic microchannel network

    Science.gov (United States)

    Moreno, Angela M.; Wilhite, Benjamin A.

    In this paper, the authors present the first demonstration of a new class of integrated ceramic microchannel reactors for all-in-one reforming of hydrocarbon fuels. The reactor concept employs precision-machined metal distributors capable of realizing complex flow distribution patterns with extruded ceramic microchannel networks for cost-effective thermal integration of multiple chemical processes. The presently reported reactor is comprised of five methanol steam reforming channels packed with CuO/γ-Al 2O 3, interspersed with four methanol combustion channels washcoated with Pt/γ-Al 2O 3, for autothermal hydrogen production (i.e., without external heating). Results demonstrate the capability of this new device for integrating combustion and steam reforming of methanol for autothermal production of hydrogen, owing to the axially self-insulating nature of distributor-packaged ceramic microchannels. In the absence of any external insulation, stable reforming of methanol to hydrogen at conversions >90% and hydrogen yields >70% was achieved at a maximum reactor temperature of 400 °C, while simultaneously maintaining a packaging temperature <50 °C.

  19. 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...

  20. Solar-hydrogen generation and solar concentration (Conference Presentation)

    NARCIS (Netherlands)

    Chinello, Enrico; Modestino, Miquel A.; Schüttauf, Jan-Willem; Lambelet, David; Delfino, Antonio; Domine, Didier; Faes, Antonin; Despeisse, Matthieu; Bailat, Julien; Psaltis, Demetri; Fernandez Rivas, David; Ballif, Christophe; Moser, Christophe; Sulima, Oleg V.; Conibeer, Gavin

    2016-01-01

    We successfully demonstrated and reported the highest solar-to-hydrogen efficiency with crystalline silicon cells and Earth-abundant electrocatalysts under unconcentrated solar radiation. The combination of hetero-junction silicon cells and a 3D printed Platinum/Iridium-Oxide electrolyzer has been p

  1. Heterogeneous platinum-catalyzed hydrogenation of dialkyl(diolefin)platinum(II) complexes: A new route to platinum surface alkyls

    OpenAIRE

    McCarthy, Thomas J.; Shih, Yen-Shiang; Whitesides, George M.

    1981-01-01

    Platinum metal catalyzes the reduction of dialkyl(diolefin)platinum(II) complexes by dihydrogen to alkanes and platinum(0). The reaction involves adsorption of the platinum(II) complex on the platinum(0) catalyst surface with conversion of the alkyl moieties to platinum surface alkyls; these appear as alkane products. The platinum atom originally present in the soluble organoplatinum species becomes part of the platinum(0) surface.

  2. 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.

  3. Next Generation Hydrogen Station Composite Data Products: Retail Stations, Data Through Quarter 3 of 2016

    Energy Technology Data Exchange (ETDEWEB)

    Sprik, Sam [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kurtz, Jennifer [National Renewable Energy Lab. (NREL), Golden, CO (United States); Ainscough, Chris [National Renewable Energy Lab. (NREL), Golden, CO (United States); Saur, Genevieve [National Renewable Energy Lab. (NREL), Golden, CO (United States); Peters, Michael [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jeffers, Matthew [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2017-03-07

    This publication includes 80 composite data products (CDPs) produced in Spring 2016 for next generation hydrogen stations, with data through the third quarter of 2016. These CDPs include data from retail stations only.

  4. 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...

  5. Continuous/Batch Mg/MgH2/H2O-Based Hydrogen Generator

    Science.gov (United States)

    Kindler, Andrew; Huang, Yuhong

    2010-01-01

    A proposed apparatus for generating hydrogen by means of chemical reactions of magnesium and magnesium hydride with steam would exploit the same basic principles as those discussed in the immediately preceding article, but would be designed to implement a hybrid continuous/batch mode of operation. The design concept would simplify the problem of optimizing thermal management and would help to minimize the size and weight necessary for generating a given amount of hydrogen.

  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 and storage from hydrolysis of sodium borohydride in batch reactors

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, A.M.F.R.; Falcao, D.S. [Departamento de Eng. Quimica, Centro de Estudos de Fenomenos de Transporte, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Silva, R.A.; Rangel, C.M. [Instituto Nacional de Engenharia e Tecnologia e Inovacao, Paco do Lumiar 22, 1649-038 (Portugal)

    2006-08-15

    The catalytic hydrolysis of alkaline sodium borohydride (NaBH{sub 4}) solution was studied using a non-noble; nickel-based powered catalyst exhibiting strong activity even after long time storage. This easy-to-prepare catalyst showed an enhanced activity after being recovered from previous use. The effects of temperature, NaBH{sub 4} concentration, NaOH concentration and pressure on the hydrogen generation rate were investigated. Particular importance has the effect of pressure, since the maximum reached pressure of hydrogen is always substantially lower than predictions (considering 100% conversion) due to solubility effects. The solubility of hydrogen is greatly enhanced by the rising pressure during reaction, leading to storage of hydrogen in the liquid phase. This effect can induce new ways of using this type of catalyst and reactor for the construction of hydrogen generators and even containers for portable and in situ applications. (author)

  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. 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

  10. Solar-hydrogen generation and solar concentration (Conference Presentation)

    Science.gov (United States)

    Chinello, Enrico; Modestino, Miguel A.; Schüttauf, Jan-Willem; Lambelet, David; Delfino, Antonio; Dominé, Didier; Faes, Antonin; Despeisse, Matthieu; Bailat, Julien; Psaltis, Demetri; Fernandez Rivas, David; Ballif, Christophe; Moser, Christophe

    2016-09-01

    We successfully demonstrated and reported the highest solar-to-hydrogen efficiency with crystalline silicon cells and Earth-abundant electrocatalysts under unconcentrated solar radiation. The combination of hetero-junction silicon cells and a 3D printed Platinum/Iridium-Oxide electrolyzer has been proven to work continuously for more than 24 hours in neutral environment, with a stable 13.5% solar-to-fuel efficiency. Since the hydrogen economy is expected to expand to a global scale, we demonstrated the same efficiency with an Earth-abundant electrolyzer based on Nickel in a basic medium. In both cases, electrolyzer and photovoltaic cells have been specifically sized for their characteristic curves to intersect at a stable operating point. This is foreseen to guarantee constant operation over the device lifetime without performance degradation. The next step is to lower the production cost of hydrogen by making use of medium range solar concentration. It permits to limit the photoabsorbing area, shown to be the cost-driver component. We have recently modeled a self-tracking solar concentrator, able to capture sunlight within the acceptance angle range +/-45°, implementing 3 custom lenses. The design allows a fully static device, avoiding the external tracker that was necessary in a previously demonstrated +/-16° angular range concentrator. We will show two self-tracking methods. The first one relies on thermal expansion whereas the second method relies on microfluidics.

  11. Ir-Catalyzed Enantioselective Hydrogenation of 2H-1,4-Benzoxazines with a Chiral 1,2,3,4- Tetrahydro-l-naphthylamine Derived Phosphine-aminophosphine Ligand

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平

    2012-01-01

    Unsymmetrical hybrid chiral phosphine-aminophosphine ligand derived from 1,2,3,4-tetrahydro-l-naphthyl- amine has been found to be highly efficient in the Ir-catalyzed asymmetric hydrogenation of various 3-aryl-2H-1,4-benzoxazines, providing good enantioselectivities (up to 95% ee) and high catalytic activity (S/C up to 5000).

  12. Efficient catalytic interconversion between NADH and NAD+ accompanied by generation and consumption of hydrogen with a water-soluble iridium complex at ambient pressure and temperature.

    Science.gov (United States)

    Maenaka, Yuta; Suenobu, Tomoyoshi; Fukuzumi, Shunichi

    2012-01-11

    Regioselective hydrogenation of the oxidized form of β-nicotinamide adenine dinucleotide (NAD(+)) to the reduced form (NADH) with hydrogen (H(2)) has successfully been achieved in the presence of a catalytic amount of a [C,N] cyclometalated organoiridium complex [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(H(2)O)](2) SO(4) [1](2)·SO(4) under an atmospheric pressure of H(2) at room temperature in weakly basic water. The structure of the corresponding benzoate complex Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))-benzoate-κC(3))(H(2)O) 2 has been revealed by X-ray single-crystal structure analysis. The corresponding iridium hydride complex formed under an atmospheric pressure of H(2) undergoes the 1,4-selective hydrogenation of NAD(+) to form 1,4-NADH. On the other hand, in weakly acidic water the complex 1 was found to catalyze the hydrogen evolution from NADH to produce NAD(+) without photoirradiation at room temperature. NAD(+) exhibited an inhibitory behavior in both catalytic hydrogenation of NAD(+) with H(2) and H(2) evolution from NADH due to the binding of NAD(+) to the catalyst. The overall catalytic mechanism of interconversion between NADH and NAD(+) accompanied by generation and consumption of H(2) was revealed on the basis of the kinetic analysis and detection of the catalytic intermediates.

  13. 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.

  14. Epoxidation of olefins and allylic alcohols with hydrogen peroxide catalyzed by heteropoly acids in the presence of cetylpyridinium chloride

    Energy Technology Data Exchange (ETDEWEB)

    Okabayashi, Takuji; Yamawaki, Kazumasa; Nishihara, Hideki; Yamada, Hiroshi; Ura, Toshikazu; Ishii, Yasutaka; Ogawa, Masaya

    1987-11-01

    The epoxidation of olefins and allylic alcohols with aqueous hydrogen peroxide could be achieved in good yield when 12-tungustophosphoric acid(WPA) was used with two phase condition using chloroform as the solvent. From the epoxidation result by 12-molybdophosphoric acid(MPA) and WPA catalysts, epoxidation activity of WPA catalyst was found to be remarkably higher than that of MPA. The rate of epoxidation by heteropoly acids catalyst depended markedly upon the activity of the reaction medium. Epoxidation of allylic alcohols with hydrogen peroxide proceeded under mild conditions, resulting good yield of epoxi-alcohols. Epoxidation of olefins by WPA/cetylpyridium chloride was confirmed to be promoted selectively with cheap and pure hydrogen peroxide, resulting good yield. (3 figs, 2 tabs, 18 refs)

  15. 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

  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. The impact of Metal-Ligand Cooperation in Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium PNP Pincer

    NARCIS (Netherlands)

    Filonenko, G.A.; Conley, M.P.; Copéret, C.; Lutz, M.; Hensen, E.J.M.; Pidko, E.A.

    2013-01-01

    The metal–ligand cooperative activation of CO2 with pyridine-based ruthenium PNP pincer catalysts leads to pronounced inhibition of the activity in the catalytic CO2 hydrogenation to formic acid. The addition of water restores catalytic performance by activating alternative reaction pathways and lea

  18. Activation of aqueous hydrogen peroxide for non-catalyzed dihydroperoxidation of ketones by azeotropic removal of water.

    Science.gov (United States)

    Starkl Renar, K; Pečar, S; Iskra, J

    2015-09-28

    Cyclic and acyclic ketones were selectively converted to gem-dihydroperoxides in 72-99% yield with 30% aq. hydrogen peroxide by azeotropic distillation of water from the reaction mixture without any catalyst. The reactions were more selective than with 100% H2O2 and due to neutral conditions also less stable products could be obtained.

  19. The mechanism of the catalytic oxidation of hydrogen sulfide *1: III. An electron spin resonance study of the sulfur catalyzed oxidation of hydrogen sulfide

    NARCIS (Netherlands)

    Steijns, M.; Koopman, P.; Nieuwenhuijse, B.; Mars, P.

    1976-01-01

    ESR experiments on the oxidation of hydrogen sulfide were performed in the temperature range 20–150 °C. Alumina, active carbon and molecular sieve zeolite 13X were investigated as catalysts. For zeolite 13X it was demonstrated that the reaction is autocatalytic and that sulfur radicals are the activ

  20. 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%.

  1. Enviro-Friendly Hydrogen Generation from Steel Mill-Scale via Metal-Steam Reforming

    Science.gov (United States)

    Azad, Abdul-Majeed; Kesavan, Sathees

    2006-01-01

    An economically viable and environmental friendly method of generating hydrogen for fuel cells is by the reaction of certain metals with steam, called metal-steam reforming (MSR). This technique does not generate any toxic by-products nor contributes to the undesirable greenhouse effect. From the standpoint of favorable thermodynamics, total…

  2. 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

  3. 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.

  4. Minimising hydrogen sulphide generation during steam assisted production of heavy oil

    OpenAIRE

    Wren Montgomery; Sephton, Mark A.; Watson, Jonathan S.; Huang Zeng; Andrew C. Rees

    2015-01-01

    The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strateg...

  5. Efficiency and economics of large scale hydrogen liquefaction. [for future generation aircraft requirements

    Science.gov (United States)

    Baker, C. R.

    1975-01-01

    Liquid hydrogen is being considered as a substitute for conventional hydrocarbon-based fuels for future generations of commercial jet aircraft. Its acceptance will depend, in part, upon the technology and cost of liquefaction. The process and economic requirements for providing a sufficient quantity of liquid hydrogen to service a major airport are described. The design is supported by thermodynamic studies which determine the effect of process arrangement and operating parameters on the process efficiency and work of liquefaction.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. Minimising hydrogen sulphide generation during steam assisted production of heavy oil

    Science.gov (United States)

    Montgomery, Wren; Sephton, Mark A.; Watson, Jonathan S.; Zeng, Huang; Rees, Andrew C.

    2015-02-01

    The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strategy. Here we use laboratory aquathermolysis to reproduce conditions that may be experienced during thermal extraction. The results indicate that hydrogen sulphide generation occurs within a specific temperature and pressure window and corresponds to chemical and physical changes in the oil. Asphaltenes are identified as the major source of sulphur. Our findings reveal that for high sulphur heavy oils, the generation of hydrogen sulphide during steam assisted thermal recovery is minimal if temperature and pressure are maintained within specific criteria. This strict pressure and temperature dependence of hydrogen sulphide release can allow access to the world's most voluminous oil deposits without generating excessive amounts of this unwanted gas product.

  12. Association of poly(ADP-ribose) polymerase with nuclear subfractions catalyzed with sodium tetrathionate and hydrogene peroxide crosslinks.

    Science.gov (United States)

    Desnoyers, S; Kirkland, J B; Poirier, G G

    1996-06-21

    Poly(ADP-ribose) polymerase (PARP) is a nuclear enzyme which catalyzes the transfer of ADP-ribose units from NAD+ to a variety of nuclear proteins under the stimulation of DNA strand break. To examine its role in DNA repair, we have been studying the interaction of PARP with other nuclear proteins using disulfide cross-linking, initiated by sodium tetrathionate (NaTT). Chinese Hamster Ovary (CHO) cells were extracted sequentially with Nonidet P40 (detergent), nucleases (DNase+RNase), and high salt (1.6 M NaCl) with and without the addition of a sulfhydryl reducing agent. The residual structures are referred to as the nuclear matrix, and are implicated in the organization of DNA repair and replication. Treatment of the cells with NaTT causes the crosslinking of PARP to the nuclear matrix. Activating PARP by pretreating the cells with H2O2 did not increase the cross-linking of PARP with the nuclear matrix, suggesting a lack of additional interaction of the enzyme with the nuclear matrix during DNA repair. Both NaTT and H2O2 induced crosslinks of PARP that were extractable with high salt. To shorten the procedure, these crosslinks were extracted from cells without nucleases and high salt treatment, using phosphate buffer. Using western blotting, these crosslinks appeared as a smear of high molecular weight species including a possible dimer of PARP at 230 kDa, which return to 116 kDa following reduction with beta-mercaptoethanol.

  13. Reversible hydrogen storage in titanium-catalyzed LiAlH{sub 4}-LiBH{sub 4} system

    Energy Technology Data Exchange (ETDEWEB)

    Mao, J.F. [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Guo, Z.P., E-mail: zguo@uow.edu.a [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); School of Mechanical, Materials and Mechatronics Engineering, University of Wollongong, NSW 2522 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Liu, H.K. [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Yu, X.B., E-mail: yuxuebin@fudan.edu.c [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia); Department of Materials Science, Fudan University, Shanghai 200433 (China)

    2009-11-13

    We have investigated the hydrogen storage properties of the LiAlH{sub 4}-LiBH{sub 4} system, both un-doped and doped with titanium based catalysts. It was found that TiF{sub 3} exhibited the superior catalytic effects in terms of enhancing the hydriding/dehydriding kinetics and reducing the dehydrogenation temperature of the LiAlH{sub 4}-LiBH{sub 4} system. Compared to the un-doped LiAlH{sub 4}-LiBH{sub 4} system, the onset temperatures of the 5 mol% TiF{sub 3}-doped sample for the first and second dehydrogenation steps were decreased by 64 and 150 deg. C, respectively. X-ray diffraction patterns of the dehydrogenated samples revealed that the produced Al from LiAlH{sub 4} could react with B from the decomposition of LiBH{sub 4} to form AlB{sub 2} and LiAl compounds. Pressure-composition-temperature (PCT) and van't Hoff plots made it clear that the decomposition enthalpy of LiBH{sub 4} in the TiF{sub 3}-doped LiAlH{sub 4}-LiBH{sub 4} system is decreased from 74 kJ/(mol of H{sub 2}) for the pure LiBH{sub 4} to 60.4 kJ/(mol of H{sub 2}). The dehydrogenation products of the TiF{sub 3}-doped LiAlH{sub 4}-LiBH{sub 4} sample can absorb 3.76 and 4.78 wt.% of hydrogen in 1 h and 14 h, respectively, at 600 deg. C and under 4 MPa of hydrogen. The formation of LiBH{sub 4} was detected by X-ray diffraction in the rehydrogenated sample.

  14. 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

    2013-08-19

    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.

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-06-07

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

  17. 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.)

  18. 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.

  19. 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.

  20. 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.

  1. Optimization and field demonstration of hybrid hydrogen generator/high efficiency furnace system

    Energy Technology Data Exchange (ETDEWEB)

    Entchev, E.; Coyle, I.; Szadkowski, F. [CANMET Energy Technology Centre, 1 Haanel Dr., Ottawa, Ontario K1A-1M1 (Canada); Manning, M.; Swinton, M. [National Research Council Ottawa, Ontario (Canada); Graydon, J.; Kirk, D. [University of Toronto, Toronto, Ontario (Canada)

    2009-05-15

    Hydrogen is seen as an energy carrier of the future and significant research on hydrogen generation, storage and utilization is accomplished around the world. However, an appropriate intermediate step before wide hydrogen introduction will be blending conventional fuels such as natural gas, oil or diesel with hydrogen and follow up combustion through conventional means. Due to changes in the combustion and flame characteristics of the system additional research is needed to access the limits and the impact of the fuel mix on the combustion systems performance. The hybrid system consists of a 5 kW{sub el} electrolyzer and a residential 15 kW{sub th} high efficiency gas fired furnace. The electrolyzer was integrated with the furnace gas supply and setup to replace 5-25% of the furnace natural gas flow with hydrogen. A mean for proper mixing of hydrogen with natural gas was provided and a control system for safe system operation was developed. Prior to the start of the field trial the hybrid system was investigated in laboratory environment. It was subjected to a variety of steady state and cycling conditions and a detailed performance and optimization analysis was performed with a range of hydrogen/natural gas mixtures. The optimized system was then installed at the Canadian Centre for Housing Technologies (CCHT) Experimental research house. The energy performance of the hybrid system was compared to the energy performance of an identical high efficiency furnace in the Control research house next door. (author)

  2. Hydrogen generation from small-scale wind-powered electrolysis system in different power matching modes

    Energy Technology Data Exchange (ETDEWEB)

    Goekcek, Murat [Department of Mechanical Engineering, Faculty of Engineering, Nigde University, Campus, 51100 Nigde (Turkey)

    2010-10-15

    This study presents a techno-economic evaluation on hydrogen generation from a small-scale wind-powered electrolysis system in different power matching modes. For the analysis, wind speed data, which measured as hourly time series in Kirklareli, Turkey, were used to predict the electrical energy and hydrogen produced by the wind-hydrogen energy system and their variation according to the height of the wind turbine. The system considered in this study is primarily consisted of a 6 kW wind-energy conversion system and a 2 kW PEM electrolyzer. The calculation of energy production was made by means of the levelized cost method by considering two different systems that are the grid-independent system and the grid-integrated system. Annual production of electrical energy and hydrogen was calculated as 15,148.26 kWh/year and 102.37 kg/year, respectively. The highest hydrogen production is obtained in January. The analyses showed that both electrical energy and hydrogen production depend strongly on the hub height of wind turbine in addition to the economic indicators. In the grid-integrated system, the calculated levelized cost of hydrogen changes in the range of 0.3485-4.4849 US$/kg for 36 m hub height related to the specific turbine cost. The grid-integrated system can be considered as profitable when the excess electrical energy delivered by system sold to the grid. (author)

  3. Flight Hydrogen Sensor for use in the ISS Oxygen Generation Assembly

    Science.gov (United States)

    MSadoques, George, Jr.; Makel, Darby B.

    2005-01-01

    This paper provides a description of the hydrogen sensor Orbital Replacement Unit (ORU) used on the Oxygen Generation Assembly (OGA), to be operated on the International Space Station (ISS). The hydrogen sensor ORU is being provided by Makel Engineering, Inc. (MEI) to monitor the oxygen outlet for the presence of hydrogen. The hydrogen sensor ORU is a triple redundant design where each sensor converts raw measurements to actual hydrogen partial pressure that is reported to the OGA system controller. The signal outputs are utilized for system shutdown in the event that the hydrogen concentration in the oxygen outlet line exceeds the specified shutdown limit. Improvements have been made to the Micro-Electro-Mechanical Systems (MEMS) based sensing element, screening, and calibration process to meet OGA operating requirements. Two flight hydrogen sensor ORUs have successfully completed the acceptance test phase. This paper also describes the sensor s performance during acceptance testing, additional tests planned to extend the operational performance calibration cycle, and integration with the OGA system.

  4. Palladium-Catalyzed Nucleophilic Substitution of Alcohols : Mechanistic Studies and Synthetic Applications

    OpenAIRE

    Sawadjoon, Supaporn

    2013-01-01

    This thesis deals with the palladium-catalyzed nucleophilic substitution of π-activated alcohols in which the C–O bond of a non-manipulated hydroxyl group is cleaved. The thesis is divided in two chapters describing two different catalytic systems. Chapter 2 describes a heterogeneous palladium-catalyzed transfer hydrogenolysis of primary, secondary, and tertiary benzylic alcohols to generate the corresponding aromatic hydrocarbons using formic acid as the hydrogen donor. A detailed mechanisti...

  5. 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)

  6. 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.

  7. 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

  8. 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

  9. Hot-Wire generated atomic hydrogen and its impact on thermal ALD in $TiCl_4/NH_3$ system

    NARCIS (Netherlands)

    Van Bui, H.; Kovalgin, A.Y.; Aarnink, A.A.I.; Wolters, R.A.M.

    2013-01-01

    We present the generation of atomic hydrogen made by the dissociation of molecular hydrogen upon collision with a tungsten (W) filament kept at a high temperature (T ≈ 1600–1900◦C). We demonstrate the ability to create atomic hydrogen and to introduce it in short pulses in experiments on etching of

  10. 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.

  11. Synthesis, characterization, and hydrogen gas sensing properties of AuNs-catalyzed ZnO sputtered thin films

    Science.gov (United States)

    Drmosh, Q. A.; Yamani, Z. H.

    2016-07-01

    Hydrogen present in concentration up to 4 vol.% forms an explosive mixture with air. Its propensity to escape in the event of leak, could lead to quick build-up and formation of an explosive mixture with air in confined spaces, such as an automobile. This necessitates its detection at very low concentration. Zinc oxide (ZnO) is a well-known wide band gap (∼3.37 eV) semiconducting oxide that has been widely used for gas sensing applications. This work reports on the fabrication, characterization and gas sensing performance of nanogold decorated ZnO thin films made by DC reactive sputtering. The sensor films were fabricated by depositing a very thin layer of gold on the sputtered ZnO thin film. The as deposited Au@ZnO films were converted into highly crystalline ZnO film covered with gold nanostructures (AuNs@ZnO) by mild heat treatment. The structural and morphological as well as the compositional homogeneity of the as-deposited and heat-treated ZnO, Au@ZnO and AuNs@ZnO thin films were ascertained. The gas sensing behavior of the AuNs@ZnO thin films towards hydrogen as a function of temperature at different H2 concentrations was investigated and compared with that of pure and heat-treated ZnO films. The effect of the presence of gold nanoparticles on imparting improvement (in terms of higher response signal, high reproducibility and complete reversibility) was established; the optimal operating temperature was about 400 °C. A plausible mechanism for the observed enhancement in the sensing behavior of AuNs@ZnO films towards H2 is proposed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Arakawa, Hidetoshi; Kanemitsu, Mahina; Tajima, Noriko; Maeda, Masako

    2002-11-20

    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{sup -7} to 10{sup -3} mol/l and sensitivity of 10{sup -8} mol/l. This method was also applied to the determination of total catechin levels in green tea, black tea and roasted green tea.

  13. 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

  14. 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

  15. Low-level hydrogen peroxide generation by unbleached cotton nonwovens: implications for wound healing applications

    Science.gov (United States)

    Greige cotton is an intact plant fiber. The cuticle and primary cell wall near the outer surface of the cotton fiber contains pectin, peroxidases, superoxide dismutase (SOD), and trace metals, which are associated with hydrogen peroxide (H2O2) generation during cotton fiber development. The compon...

  16. 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

  17. 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.

  18. 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

  19. Simultaneous in situ generation of hydrogen peroxide and Fenton reaction over Pd-Fe catalysts

    OpenAIRE

    Yalfani, Mohammad S.; Contreras, Sandra; Llorca Piqué, Jordi; Domínguez Escalante, Montserrat; Sueiras, Jesús; Medina, Francesc

    2010-01-01

    High mineralization degree of organic compounds can be achieved by a novel environmentally-friendly full heterogeneous Pd–Fe catalytic system, which involves in situ generation of hydrogen peroxide from formic acid and oxygen, and oxidation of organic compounds by Fenton process in a one-pot reaction.

  20. 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...

  1. 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.''

  2. Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks.

    Science.gov (United States)

    Martins, Luísa; Nasani, Rajendar; Saha, Manideepa; Mobin, Shaikh; Mukhopadhyay, Suman; Pombeiro, Armando

    2015-10-21

    Microwave assisted synthesis of the Cu(I) compound [Cu(µ₄-4-ptz)]n [1, 4-ptz=5-(4-pyridyl)tetrazolate] 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-ptz)₄(µ₂-N₃)₂(DMF)₂]n∙(DMF)2n (2) and [Cu(µ₂-4-ptz)₂(H₂O)₂]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.

  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. Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 1: Copper-Catalyzed Oxidation.

    Science.gov (United States)

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

    2016-05-25

    Sulfidic off-odors as a result of hydrogen sulfide (H2S) and low-molecular-weight thiols are commonly encountered in wine production. These odors are usually removed by the process of Cu(II) fining, a process that remains poorly understood. The present study aims to elucidate the underlying mechanisms by which Cu(II) interacts with H2S and thiol compounds (RSH) under wine-like conditions. Copper complex formation was monitored along with H2S, thiol, oxygen, and acetaldehyde concentrations after the addition of Cu(II) (50 or 100 μM) to air-saturated model wine solutions containing H2S, cysteine, 6-sulfanylhexan-1-ol, or 3-sulfanylhexan-1-ol (300 μM each). The presence of H2S and thiols in excess to Cu(II) led to the rapid formation of ∼1.4:1 H2S/Cu and ∼2:1 thiol/Cu complexes, resulting in the oxidation of H2S and thiols and reduction of Cu(II) to Cu(I), which reacted with oxygen. H2S was observed to initially oxidize rather than form insoluble copper sulfide. The proposed reaction mechanisms provide insight into the extent to which H2S can be selectively removed in the presence of thiols in wine.

  5. 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.

  6. 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...

  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. Helium-3 Generation from the Interaction of Deuterium Plasma inside a Hydrogenated Lattice: Red Fusion

    Science.gov (United States)

    Leal-Quiros, Edbertho; Leal-Escalante, David A.

    2015-03-01

    Helium-3 has been created in a nuclear fusion reaction by fusing deuterium ions from deuterium plasma with hydrogen ions in a “RED” (the Spanish word for net) or crystal lattice, a method we called red fusion ("Fusion en la red cristalina"), because is a new method to make nuclear fusion reaction. In this paper, it will be show the experimental results where the helium-3 has been generated for the first time in this kind of new method to confine deuterium and hydrogen inside the RED or lattice of the hydrogenated crystal and that confinement inside the RED facilitated overcoming the Coulomb barrier between them and helium-3 and phonons are produced in this fusion reaction. The results of a long time research in which helium-3, has been created in a fusion reaction inside the lattice or RED of the crystal that contained hydrogen after adequate interaction of deuterium plasma at appropriate high temperature and magnetic confinement of the Mirror/Cusp Plasma Machine at Polytechnic University of Puerto Rico, designed by the authors. Several mass spectra and visible light spectrum where the presence of helium-3 was detected are shown. The experiment was repeated more than 200 times showing always the generation of helium-3. In this experiment no gamma rays were detected. For this experiment several diagnostic instruments were used. The data collection with these control instrumentation are shown. Thus, it is an important new way to generate Helium-3. reserved.

  9. 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)

  10. 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

  11. 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.

  12. 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.

  13. Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

    Science.gov (United States)

    Kindler, Andrew; Huang, Yuhong

    2010-01-01

    Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

  14. Lens Endogenous Peptide αA66-80 Generates Hydrogen Peroxide and Induces Cell Apoptosis.

    Science.gov (United States)

    Raju, Murugesan; Santhoshkumar, Puttur; Sharma, K Krishna

    2017-02-01

    In previous studies, we reported the presence of a large number of low-molecular-weight (LMW) peptides in aged and cataract human lens tissues. Among the LMW peptides, a peptide derived from αA-crystallin, αA66-80, was found in higher concentration in aged and cataract lenses. Additional characterization of the αA66-80 peptide showed beta sheet signature, and it formed well-defined unbranched fibrils. Further experimental data showed that αA66-80 peptide binds α-crystallin, impairs its chaperone function, and attracts additional crystallin proteins to the peptide α-crystallin complex, leading to the formation of larger light scattering aggregates. It is well established that Aβ peptide exhibits cell toxicity by the generation of hydrogen peroxide. The αA66-80 peptide shares the principal properties of Aβ peptide. Therefore, the present study was undertaken to determine whether the fibril-forming peptide αA66-80 has the ability to generate hydrogen peroxide. The results show that the αA66-80 peptide generates hydrogen peroxide, in the amount of 1.2 nM H2O2 per µg of αA66-80 peptide by incubation at 37°C for 4h. We also observed cytotoxicity and apoptotic cell death in αA66-80 peptide-transduced Cos7 cells. As evident, we found more TUNEL-positive cells in αA66-80 peptide transduced Cos7 cells than in control cells, suggesting peptide-mediated cell apoptosis. Additional immunohistochemistry analysis showed the active form of caspase-3, suggesting activation of the caspase-dependent pathway during peptide-induced cell apoptosis. These results confirm that the αA66-80 peptide generates hydrogen peroxide and promotes hydrogen peroxide-mediated cell apoptosis.

  15. Hydrogen peroxide catalytic decomposition

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2010-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

  16. 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.

  17. Hydrogen generation from sodium borohydride solution using a ruthenium supported on graphite catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Yan; Dai, Hong-Bin; Ma, Lai-Peng; Wang, Ping; Cheng, Hui-Ming [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)

    2010-04-15

    The catalyst with high activity and durability plays a crucial role in the hydrogen generation systems for the portable fuel cell generators. In the present study, a ruthenium supported on graphite catalyst (Ru/G) for hydrogen generation from sodium borohydride (NaBH{sub 4}) solution is prepared by a modified impregnation method. This is done by surface pretreatment with NH{sub 2} functionalization via silanization, followed by adsorption of Ru (III) ion onto the surface, and then reduced by a reducing agent. The obtained catalyst is characterized by transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). Very uniform Ru nanoparticles with sizes of about 10 nm are chemically bonded on the graphite surface. The hydrolysis kinetics measurements show that the concentrations of NaBH{sub 4} and NaOH all exert considerable influence on the catalytic activity of Ru/G catalyst towards the hydrolysis reaction of NaBH{sub 4}. A hydrogen generation rate of 32.3 L min{sup -1} g{sup -1} (Ru) in a 10 wt.% NaBH{sub 4} + 5 wt.% NaOH solution has been achieved, which is comparable to other noble catalysts that have been reported. (author)

  18. Photocatalytic hydrogen generation from water under visible light using core/shell nano-catalysts.

    Science.gov (United States)

    Wang, X; Shih, K; Li, X Y

    2010-01-01

    A microemulsion technique was employed to synthesize nano-sized photocatalysts with a core (CdS)/shell (ZnS) structure. The primary particles of the photocatalysts were around 10 nm, and the mean size of the catalyst clusters in water was about 100 nm. The band gaps of the catalysts ranged from 2.25 to 2.46 eV. The experiments of photocatalytic H(2) generation showed that the catalysts (CdS)(x)/(ZnS)(1-x) with x ranging from 0.1 to 1 were able to produce hydrogen from water photolysis under visible light. The catalyst with x=0.9 had the highest rate of hydrogen production. The catalyst loading density also influenced the photo-hydrogen production rate, and the best catalyst concentration in water was 1 g L(-1). The stability of the nano-catalysts in terms of size, morphology and activity was satisfactory during an extended test period for a specific hydrogen production rate of 2.38 mmol g(-1) L(-1) h(-1) and a quantum yield of 16.1% under visible light (165 W Xe lamp, lambda>420 nm). The results demonstrate that the (CdS)/(ZnS) core/shell nano-particles are a novel photo-catalyst for renewable hydrogen generation from water under visible light. This is attributable to the large band-gap ZnS shell that separates the electron/hole pairs generated by the CdS core and hence reduces their recombinations.

  19. 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.

  20. 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.

  1. Oxygen dependency of one-electron reactions generating ascorbate radicals and hydrogen peroxide from ascorbic acid.

    Science.gov (United States)

    Boatright, William L

    2016-04-01

    The effect of oxygen on the two separate one-electron reactions involved in the oxidation of ascorbic acid was investigated. The rate of ascorbate radical (Asc(-)) formation (and stability) was strongly dependent on the presence of oxygen. A product of ascorbic acid oxidation was measurable levels of hydrogen peroxide, as high as 32.5 μM from 100 μM ascorbic acid. Evidence for a feedback mechanism where hydrogen peroxide generated during the oxidation of ascorbic acid accelerates further oxidation of ascorbic acid is also presented. The second one-electron oxidation reaction of ascorbic acid leading to the disappearance of Asc(-) was also strongly inhibited in samples flushed with argon. In the range of 0.05-1.2 mM ascorbic acid, maximum levels of measurable hydrogen peroxide were achieved with an initial concentration of 0.2 mM ascorbic acid. Hydrogen peroxide generation was greatly diminished at ascorbic acid levels of 0.8 mM or above.

  2. 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)

  3. High-purity hydrogen generation by ultraviolet illumination with the membrane composed of titanium dioxide nanotube array and Pd layer

    Science.gov (United States)

    Hattori, Masashi; Noda, Kei; Matsushige, Kazumi

    2011-09-01

    High-purity hydrogen generation was observed by using a membrane composed of a bilayer of an anodized titanium dioxide nanotube array (TNA) and a hydrogen permeable metal. This membrane was fabricated by transferring a TNA embedded in a titanium foil onto a sputtered 10-μm-thick palladium film. Alcohols are reformed photocatalytically and concurrently generated hydrogen is purified through the Pd layer. H2 with a purity of more than 99% was obtained from liquid alcohols under ultraviolet illumination onto the membrane. Thus, we demonstrated the integration of photocatalytic hydrogen production and purification within a single membrane.

  4. 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

    Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. 13C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparati....... This was demonstrated in the Ni-catalyzed Heck reaction with aryl triflates and benzyl chlorides, as well as Ru-mediated enyne metathesis....

  5. 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.

  6. Photoassisted electrolysis of water for hydrogen generation with TiO{sub 2} aggregate film

    Energy Technology Data Exchange (ETDEWEB)

    Cao Guanying [Research Institute of Photonics, Dalian Polytechnic University, Dalian, 116034 (China); Zhang Qifeng; Liu Dawei; Xi Junting; Cao Guozhong, E-mail: gzcao@uw.edu, E-mail: gycao@dlpu.edu.cn [Department of Materials Science and Engineering, University of Washington, Seattle, 98195 (United States)

    2011-02-01

    In this paper, the nanocrystallite aggregates of TiO{sub 2} were synthesized and characterized by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Brunauer-Emmett-Teller (BET). The aggregates are of submicron size, formed by nano-sized crystallites and able to offer both a large specific surface area and desirable size comparable to the wavelength of visible light. Therefore, the TiO{sub 2} aggregates were also studied as photoelectrode in photoelectrochemical cell for hydrogen generation. The results show that the hydrogen generation rates are 0.47 ml/h*cm{sup 2} and 0.27 ml/h*cm{sup 2} during the first test with and without illumination, respectively. The current density also presented continually increasing during the light-on period. This was attributed to the photogenerated current, which benefited from the TiO{sub 2} aggregates and may significantly enhance the electrolysis rate of water.

  7. Radcalc for Windows 2.0 transportation packaging software to determine hydrogen generation and transportation classification

    Energy Technology Data Exchange (ETDEWEB)

    Green, J.R.

    1996-10-21

    Radclac for Windows is a user friendly menu-driven Windows compatible software program with applications in the transportation of radioactive materials. It calculates the radiolytic generation of hydrogen gas in the matrix of low-level and high-level radioactive wastes. It also calculates pressure buildup due to hydrogen and the decay heat generated in a package at seal time. It computes the quantity of a radionuclide and its associated products for a given period of time. In addition, the code categorizes shipment quantities as reportable quantity (RQ), radioactive Type A or Type B, limited quality (LQ), low specific activity (LSA), highway road controlled quality (HRCQ), and fissile excepted using US Department of Transportation (DOT) definitions and methodologies.

  8. Towards numerical simulation of turbulent hydrogen combustion based on flamelet generated manifolds in OpenFOAM

    Science.gov (United States)

    Fancello, A.; Bastiaans, R. J. M.; de Goey, L. P. H.

    2013-10-01

    This work proposes an application of the Flamelet-Generated Manifolds (FGM) technique in the OpenFOAM environment. FGM is a chemical reduced method for combustion modeling. This technique treats the combustion process as the solution of a small amount of controlling variables. Regarding laminar simulation, a progress variable and enthalpy evolution can describe satisfactorily the problem. From a turbulent point of view, FGM can be applied to LES and RANS simulations, where the subgrid chemical terms are described with a β - PDF approach. These approaches apply satisfactorily in relatively simple gases, nevertheless for hydrogen are not more valid, due to preferential diffusion effects and instability of the flame structure. The overall aim of this research is to find technical solution for hydrogen gas turbines design in the next generation of Integrated Gasification Combined Cycle (IGCC) plants.

  9. 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.

  10. 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.

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

    Science.gov (United States)

    Ly, Ngoc Tai; Hoa Dao, Thi; Hoang To, Le Hong; Vu, Dinh Lam; Le, Van Hong

    2014-09-01

    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.

  12. 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.

  13. Hydrocarbon reforming catalysts and new reactor designs for compact hydrogen generators

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, A.; Schwab, E.; Urtel, H. [BASF SE, Ludwigshafen (Germany); Farrauto, R. [BASF Catalysts LLC, Iselin, NJ (United States)

    2010-12-30

    A hydrogen based future energy scenario will use fuel cells for the conversion of chemically stored energy into electricity. Depending upon the type of fuel cell, different specifications will apply for the feedstock which is converted in the cell, ranging from very clean hydrogen for PEM-FC's to desulfurized methane for SOFC and MCFC technology. For the foreseeable future, hydrogen will be supplied by conventional reforming, however operated in compact and dynamic reformer designs. This requires that known catalyst formulations are offered in specific geometries, giving flexibility for novel reactor design options. These specific geometries can be special tablet shapes as well as monolith structures. Finally, also nonhydrocarbon feedstock might be used in special applications, e.g. bio-based methanol and ethanol. BASF offers catalysts for the full process chain starting from feedstock desulfurization via reforming, high temperature shift, low temperature shift to CO fine polishing either via selective oxidation or selective methanation. Depending upon the customer's design, most stages can be served either with precious metal based monolith solutions or base metal tablet solutions. For the former, we have taken the automobile catalyst monolith support and extended its application to the fuel cell hydrogen generation. Washcoats of precious metal supported catalysts can for example be deposited on ceramic monoliths and/or metal heat exchangers for efficient generation of hydrogen. Major advantages are high through puts due to more efficient heat transfer for catalysts on metal heat exchangers, lower pressure drop with greater catalyst mechanical and thermal stability compared to particulate catalysts. Base metal tablet catalysts on the other hand can have intrinsic cost advantages, larger fractions of the reactor can be filled with active mass, and if produced in unconventional shape, again novel reactor designs are made possible. Finally, if it comes to

  14. 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)

  15. 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.

  16. White-light emission from solid carbon in aqueous solution during hydrogen generation induced by nanosecond laser pulse irradiation

    Science.gov (United States)

    Akimoto, Ikuko; Yamamoto, Shota; Maeda, Kosuke

    2016-07-01

    We previously discovered a novel method of hydrogen generation from high-grade charcoal in an aqueous solution using nanosecond laser pulse irradiation. In this paper, white-light emission during this reaction is reported: A broad spectrum over the visible range is observed above a threshold excitation energy density. The white-light emission is a simultaneous product of the hydrogen generation reaction and is attributed to blackbody radiation in accordance with Planck's Law at a temperature above 3800 K. Consequently, we propose that hydrogen generation induced by laser irradiation proceeds similarly to classical coal gasification, which features reactions at high pressure and high temperature.

  17. 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.

  18. The ZECOMIX experimental facility for hydrogen and power generation from coal

    Energy Technology Data Exchange (ETDEWEB)

    A. Calabro; P. Deiana; P. Fiorini; S. Stendardo; G. Girardi [ENEA - Italian Agency for New Technologies, Rome (Italy). Energy and Environment Energy and Plants Division

    2006-07-01

    The Zecomix project, conceived by ENEA in the framework of Italian National Hydrogen Project, is aimed at studying an integrated process that produces both hydrogen and electricity from coal, with zero emissions and very high efficiency. The Zero Emission Coal Mixed technology concept combines two different systems: the Zero Emission Coal gasification and the Zero Emission Combustion Technology based on Hydrogen-fuelled internal combustion turbine cycle. The key element is the integration of a gasification process, characterized by coal hydrogasification technology and carbon dioxide sequestration, with the power island, where an oxy-combustion occurs. The experimental facility will be realized at the ENEA Research Centre of Casaccia at about thirty kilometres from the centre of Rome. It consists of a very flexible plant, in which more components can be tested separately or connected together. The plant is provided with an atmospheric fixed bed gasifier coal and a carbonator/calcinator reactor; moreover a pressurized hydrogasifier reactor and a 100 kWe microturbine test bench are present. Other auxiliary components are a gas mixing system, for hydrogen-based syngas production, and a 200 kW steam generator. 5 refs., 5 figs., 1 tab.

  19. 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.

  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. Generation Performance of a Fuel Cell Using Hydrogen and Di-methyl-ether (DME) Mixed Gas

    Science.gov (United States)

    Haraguchi, Tadao; Watanabe, Takashi; Yamashita, Masahiro; Tsutsumi, Yasuyuki; Yamashita, Susumu

    Di-methyl-ether (DME), an oxygenated hydrocarbon, can facilitate hydrogen manufacture by steam reforming reaction at low temperature. Methanol and DME steam reforming at 250-300°C, reforming DME into hydrogen, can be performed easily with small-scale and simple equipment. Whether the hydrogen output from the reformer for supply to the fuel cell includes DME, and how this affects the generation performance has yet to be confirmed. The purpose of this paper is to investigate the supply of a fuel cell with mixtures of DME and H2 in varying proportions and to clarify the effect on generation performance. Conclusions are as follows: (1) For a supply of DME and H2 mixed gas, DME is consumed after the H2 is consumed. By comparing the experimental values with theoretical values of consumption of pure H2, a mixture of DME and H2, and pure DME, it proved to be possible to roughly predict the experimental values by calculation. (2) The voltage value moved to near the DME voltage after the H2 was consumed, the current density increased after the H2 was consumed. (3) During continuous running the voltage load was observed to fluctuate.

  2. 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.

  3. 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

  4. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-22

    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.

  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

    Energy Technology Data Exchange (ETDEWEB)

    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. 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

  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. [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.

  11. 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.

  12. 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.

  13. Endogenous generation of hydrogen sulfide and its regulation in Shewanella oneidensis

    Directory of Open Access Journals (Sweden)

    Genfu eWu

    2015-04-01

    Full Text Available Hydrogen sulfide (H2S has been recognized as a physiological mediator with a variety of functions across all domains of life. In this study, mechanisms of endogenous H2S generation in Shewanella oneidensis were investigated. As a research model with highly diverse anaerobic respiratory pathways, the microorganism is able to produce H2S by respiring on a variety of sulfur-containing compounds with SirACD and PsrABC enzymatic complexes, as well as through cysteine degradation with three enzymes, MdeA, SO_1095, and SseA. We showed that the SirACD and PsrABC complexes, which are predominantly, if not exclusively, responsible for H2S generation via respiration of sulfur species, do not interplay with each other. Strikingly, a screen for regulators controlling endogenous H2S generation by transposon mutagenesis identified global regulator Crp to be essential to all H2S-generating processes. In contrast, Fnr and Arc, two other global regulators that have a role in respiration, are dispensable in regulating H2S generation via respiration of sulfur species. Interestingly, Arc is involved in the H2S generation through cysteine degradation by repressing expression of the mdeA gene. We further showed that expression of the sirA and psrABC operons is subjected to direct regulation of Crp, but the mechanisms underlying the requirement of Crp for H2S generation through cysteine degradation remain elusive.

  14. Hydrogen generation through indirect biophotolysis in batch cultures of the nonheterocystous nitrogen-fixing cyanobacterium Plectonema boryanum.

    Science.gov (United States)

    Huesemann, Michael H; Hausmann, Tom S; Carter, Blaine M; Gerschler, Jared J; Benemann, John R

    2010-09-01

    The nitrogen-fixing nonheterocystous cyanobacterium Plectonema boryanum was used as a model organism to study hydrogen generation by indirect biophotolysis in nitrogen-limited batch cultures that were continuously illuminated and sparged with argon/CO(2) to maintain anaerobiosis. The highest hydrogen-production rate (i.e., 0.18 mL/mg day or 7.3 micromol/mg day) was observed in cultures with an initial medium nitrate concentration of 1 mM at a light intensity of 100 micromol/m(2) s. The addition of photosystem II (PSII) inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) did not reduce hydrogen-production rates relative to unchallenged controls for 50 to 150 h, and intracellular glycogen concentrations decreased significantly during the hydrogen generation period. The insensitivity of the hydrogen-production process to DCMU is indicative of the fact that hydrogen was not derived from water splitting at PSII (i.e., direct biophotolysis) but rather from electrons provided by intracellular glycogen reserves (i.e., indirect biophotolysis). It was shown that hydrogen generation could be sustained for long time periods by subjecting the cultures to alternating cycles of aerobic, nitrogen-limited growth and anaerobic hydrogen production.

  15. 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.

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

    Science.gov (United States)

    Hatzell, Marta C; Ivanov, Ivan; Cusick, Roland D; Zhu, Xiuping; Logan, Bruce E

    2014-01-28

    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.

  17. Integration of direct carbon and hydrogen fuel cells for highly efficient power generation from hydrocarbon fuels

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Choi, Pyoungho; Smith, Franklyn; Bokerman, Gary [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922-5703 (United States)

    2010-02-15

    In view of impending depletion of hydrocarbon fuel resources and their negative environmental impact, it is imperative to significantly increase the energy conversion efficiency of hydrocarbon-based power generation systems. The combination of a hydrocarbon decomposition reactor with a direct carbon and hydrogen fuel cells (FC) as a means for a significant increase in chemical-to-electrical energy conversion efficiency is discussed in this paper. The data on development and operation of a thermocatalytic hydrocarbon decomposition reactor and its coupling with a proton exchange membrane FC are presented. The analysis of the integrated power generating system including a hydrocarbon decomposition reactor, direct carbon and hydrogen FC using natural gas and propane as fuels is conducted. It was estimated that overall chemical-to-electrical energy conversion efficiency of the integrated system varied in the range of 49.4-82.5%, depending on the type of fuel and FC used, and CO{sub 2} emission per kW{sub el}h produced is less than half of that from conventional power generation sources. (author)

  18. Final Technical Report for GO15056 Millennium Cell: Development of an Advanced Chemical Hydrogen Storage and Generation System

    Energy Technology Data Exchange (ETDEWEB)

    Moreno, Oscar [Millennium Cell Inc., Eatontown, NJ (United States)

    2017-02-22

    The objectives of this project are to increase system storage capacity by improving hydrogen generation from concentrated sodium borohydride, with emphasis on reactor and system engineering; to complete a conceptual system design based on sodium borohydride that will include key technology improvements to enable a hydrogen fuel system that will meet the systembased storage capacity of 1.2 kWh/L (36 g H2/L) and 1.5 kWh/kg (45 g H2/kg), by the end of FY 2007; and to utilize engineering expertise to guide Center research in both off-board chemical hydride regeneration and on-board hydrogen generation systems.

  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. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Hydrothermal Synthesis of Co-Ru Alloy Particle Catalysts for Hydrogen Generation from Sodium Borohydride

    Directory of Open Access Journals (Sweden)

    Marija Kurtinaitienė

    2013-01-01

    Full Text Available We report the synthesis of μm and sub-μm-sized Co, Ru, and Co-Ru alloy species by hydrothermal approach in the aqueous alkaline solutions (pH ≥ 13 containing CoCl2 and/or RuCl3, sodium citrate, and hydrazine hydrate and a study of their catalytic properties for hydrogen generation by hydrolysis of sodium borohydride solution. This way provides a simple platform for fabrication of the ball-shaped Co-Ru alloy catalysts containing up to 12 wt% Ru. Note that bimetallic Co-Ru alloy bowls containing even 7 at.% Ru have demonstrated catalytic properties that are comparable with the ones of pure Ru particles fabricated by the same method. This result is of great importance in view of the preparation of cost-efficient catalysts for hydrogen generation from borohydrides. The morphology and composition of fabricated catalyst particles have been characterized using scanning electron microscopy, energy dispersive X-ray diffraction, and inductively coupled plasma optical emission spectrometry.

  8. 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.

  9. The use of renewable energy in the form of methane via electrolytic hydrogen generation using carbon dioxide as the feedstock

    Science.gov (United States)

    Hashimoto, Koji; Kumagai, Naokazu; Izumiya, Koichi; Takano, Hiroyuki; Shinomiya, Hiroyuki; Sasaki, Yusuke; Yoshida, Tetsuya; Kato, Zenta

    2016-12-01

    The history reveals the continuous increase in world energy consumption and carbon emissions. For prevention of intolerable global warming and complete exhaustion of fossil fuels we need complete conversion from fossil fuel consumption to renewable energy. We have been performing the research and development of global carbon dioxide recycling for more than 25 years to supply renewable energy to the world in the form of methane produced by the reaction of carbon dioxide captured from chimney with hydrogen generated electrolytically using electricity generated by renewable energy. We created the cathode and anode for electrolytic hydrogen generation and the catalyst for carbon dioxide methanation by the reaction with hydrogen. The methane formation from renewable energy will be the most convenient and efficient key technology for the use of renewable energy by storage of intermittent and fluctuating electricity generated from renewable energy and by regeneration of stable electricity. Domestic and international cooperation of companies for industrialization is in progress.

  10. 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.

  11. Trehalose enhancing microbial electrolysis cell for hydrogen generation in low temperature (0 °C).

    Science.gov (United States)

    Xu, Linji; Liu, Wenzong; Wu, Yining; Lee, Poheng; Wang, Aijie; Li, Shuai

    2014-08-01

    This work explored the feasibility of a method combining physical (sonication and base) and biological (partial fermentation) processes for sludge treatment and the effects of trehalose on the hydrogen generation of microbial electrolysis cell at 0 °C. The results demonstrated that the above pretreatment method was favorable, which promoted organics decomposing into lower molecular weight matter. The promotion of trehalose for MEC efficiency was obvious and the optimal concentration of trehalose was 50 mmol/L. With this concentration, the highest hydrogen recovery rate was 0.25 m(3)-H₂/-m(3)-reactor per day. Coulomb efficiency and energy recovery efficiency were 46.4% and 203%, respectively. Further, the consumption order of mixed substances was VFAs>proteins>carbohydrates. For microorganism community, SEM photographs illustrated that the selectivity of environmental temperature for the species of anode bacteria was strong and denaturing gradient gel electrophoresis indicated that Microbacterium and Proteobacteria were the two main species and Proteobacteria may be one of the species that produced electrons.

  12. 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.

  13. Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

    Directory of Open Access Journals (Sweden)

    Hongbin Dai

    2017-02-01

    Full Text Available The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine (N2H4·H2O as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO2 matrix. The Ni-Ir/CeO2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N2H4·H2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.

  14. 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

  15. Photocatalytic hydrogen generation over lanthanum doped TiO2 under UV light irradiation.

    Science.gov (United States)

    Liu, Y; Xie, L; Li, Y; Qu, J L; Zheng, J; Li, X G

    2009-02-01

    TiO2 nanoparticles doped with different amount of lanthanum were obtained by sol-gel approach and followed annealing at different temperature. The crystal size of TiO2 doped with lanthanum was smaller than that of pure TiO2. Photocatalytic activity of TiO2 doped with lanthanum for water splitting into H2 was investigated. The photocatalytic activity of TiO2 doped with lanthanum for water splitting into H2 is higher than that of pure TiO2. It was found that the optimal photocatalyst was TiO2 doped with 2 wt% lanthanum and calcined at 600 degrees C for 4 h which had hydrogen generation rate 700.6 micromol h(-1).

  16. An Innovative Test Platform for Hydrogen Production and Zero Emission Power Generation from Coal

    Energy Technology Data Exchange (ETDEWEB)

    Calabro A; Deiana P; Fiorini P; Stendardo S; Girardi G [ENEA - Italian Agency for New Technologies, Energy and Environment Energy and Plants Division - Via Anguillarese - 301 00060 S Maria di Galeria - Rome (Italy)

    2006-07-01

    The ZECOMIX project, conceived by ENEA in the framework of Italian National Hydrogen Project, is aimed at studying an integrated process that produces both hydrogen and electricity from coal, with zero emissions and very high efficiency. The key element is the integration of a gasification process, characterized by coal hydro-gasification technology and carbon dioxide sequestration, with the power island, where an oxy-combustion occurs. Many optimization analysis and simulations have been carried out demonstrating the possibility to achieve very high net efficiencies (higher than 50% LHV) and very low (quasi-zero) emissions. The project schedule consists of the design, already started, the construction and the operation of an experimental facility finalized to demonstrate the feasibility of the described reference process. The facility will be realized in the ENEA Research Center of Casaccia, near Rome. It consists of a very flexible plant, in which more components can be tested separately or connected together. The plant is provided with a 50 kg/h coal atmospheric fluid bed gasifier, a fluid bed decarbonator/calcinator reactor filled with calcium oxide pellets, a pressurized hydro-gasifier reactor characterized by a pressure variable from 30 to 100 bar, a 100 kWe micro-turbine test bench, with the combustor chamber modified because of de-carbonized syngas fuelling and finally an oxygen/hydrogen combustor test bench, for experimental activities about the definition of stability limits, operative conditions (dilution, temperature pattern, chemicals) and combustion control. Other auxiliary components are mixing station for hydrogen-based syngas production, and an ordinary steam generator. The first part of the research project is aimed at testing the single component, in particular the main preliminary design criteria adopted for hydro-gasification reactor and carbonator reactor are presented in this paper. The second part of the Project is focused on the integration

  17. A novel power generation system based on combination of hydrogen and direct carbon fuel cells for decentralized applications

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; Choi, Pyoungho; Bokerman, Gary [Central Florida Univ., FL (United States)

    2010-07-01

    Fuel cell (FC) based power generation systems are characterized by highest chemical-toelectrical (CTE) energy conversion efficiency compared to conventional power generators (e.g., internal combustion and diesel engines, turbines). Most efforts in this area relate to hydrogen-FC coupled with hydrocarbon fuel reformers (HFR). However, the overall CTE efficiency of the combined HFR-FC systems is relatively low (about 30-35%). The objective of this work is to develop a highly-efficient power generation system integrating a hydrocarbon decomposition reactor (HDR) with both hydrogen and direct-carbon FC. A unique feature of direct carbon FC is that its theoretical CTE efficiency is close to 100% and the practical efficiency could rich 80-90%. The concept of the integrated hydrogen and direct carbon FC system is discussed and the experimental data on the performance testing of a HDR coupled with PEM FC are presented in this paper. (orig.)

  18. CYP-450 isoenzymes catalyze the generation of hazardous aromatic amines after reaction with the azo dye Sudan III

    OpenAIRE

    Zanoni, Thalita Boldrin; Lizier, Thiago M. [UNESP; Assis,Marilda das Dores; Zanoni, Maria Valnice Boldrin; de Oliveira, Danielle Palma

    2013-01-01

    This work describes the mutagenic response of Sudan III, an adulterant food dye, using Salmonella typhimurium assay and the generation of hazardous aromatic amines after different oxidation methods of this azo dye. For that, we used metabolic activation by S9, catalytic oxidation by ironporphyrin and electrochemistry oxidation in order to simulate endogenous oxidation conditions. The oxidation reactions promoted discoloration from 65% to 95% of Sudan III at 1×10-4molL-1 and generation of 7.6×...

  19. Ex Situ Generation of Stoichiometric and Substoichiometric 12CO and 13CO and Its Efficient Incorporation in Palladium Catalyzed Aminocarbonylations

    DEFF Research Database (Denmark)

    Hermange, Philippe; Lindhardt, Anders Thyboe; Taaning, Rolf Hejle;

    2011-01-01

    to the development of a new solid, stable, and easy to handle source of CO for chemical transformations. The synthesis of this CO-precursor also provided an entry point for the late installment of an isotopically carbon-labeled acid chloride for the subsequent release of gaseous [13C]CO. In combination with studies...... is safely handled and stored. Furthermore, since the CO is generated ex situ, excellent functional group tolerance is secured in the carbonylation chamber. Finally, CO is only generated and released in minute amounts, hence, eliminating the need for specialized equipment such as CO-detectors and equipment...

  20. 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.

  1. 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

  2. In-situ catalyzation approach for enhancing the hydrogenation/dehydrogenation kinetics of MgH2 powders with Ni particles

    Science.gov (United States)

    El-Eskandarany, M. Sherif; Shaban, Ehab; Ali, Naser; Aldakheel, Fahad; Alkandary, Abdullah

    2016-11-01

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation.

  3. Efficiency in chemistry: from hydrogen autotransfer to multicomponent catalysis.

    Science.gov (United States)

    Alonso, Francisco; Foubelo, Francisco; González-Gómez, José C; Martínez, Ricardo; Ramón, Diego J; Riente, Paola; Yus, Miguel

    2010-08-01

    A hydrogen autotransfer reaction has been applied to the α-alkylation of ketones, with primary alcohols as the electrophilic component, either under homogeneous (using a Ru complex as catalyst) or under heterogeneous (using Ni nanoparticles) conditions. This process is both very efficient (concerning atom economy) and ecologically friendly (water as the only by-product generated). On the other hand, three multicomponent reactions, namely, the Strecker reaction (without any catalyst), the aza-Sakurai process (catalyzed by ferrite), and the addition of in situ generated Zn enolates to chiral sulfinylimines (catalyzed by Cu), have proven to be very efficient in the generation of a diversity of polyfunctionalized molecules.

  4. 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

  5. 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.

  6. Hydrogen peroxide generation and photocatalytic degradation of estrone by microstructural controlled ZnO nanorod arrays

    Energy Technology Data Exchange (ETDEWEB)

    Liu Yangsi; Han Jie; Qiu Wei [Department of Chemical and Materials Engineering, The University of Auckland, Private Bag 92019, Auckland 1142 (New Zealand); Gao Wei, E-mail: w.gao@auckland.ac.nz [Department of Chemical and Materials Engineering, The University of Auckland, Private Bag 92019, Auckland 1142 (New Zealand)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer H{sub 2}O{sub 2} generated by ZnO nanorod arrays during UV irradiation was detected. Black-Right-Pointing-Pointer ZnO nanorod arrays were synthesized via a facile hydrothermal technique. Black-Right-Pointing-Pointer The microstructure can be controlled by varying reactants' concentration. Black-Right-Pointing-Pointer Photocatalytic degradation of estrone by ZnO nanorod arrays was studied. Black-Right-Pointing-Pointer Microstructures' effect on photocatalysis and H{sub 2}O{sub 2} generation was discussed. - Abstract: The strong oxidant, hydrogen peroxide (H{sub 2}O{sub 2}), generated by ZnO nanorod arrays under UV light irradiation was monitored by fluorescence analysis. The ZnO nanorod arrays were synthesized via a low temperature hydrothermal method and their dimensions, i.e., diameter and height, can be controlled by adjusting the concentration of zinc nitrate (Zn(NO{sub 3}){sub 2}{center_dot}6H{sub 2}O) and hexamethylenetetramine (HMT). The morphology, nanostructure, surface roughness and optical property were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM) and transmittance spectra, respectively. The ZnO nanorod arrays were applied in the degradation of estrone, which is an emerging steroid estrogen contaminant. The results revealed that the ZnO nanorod array produced from 25 mM Zn{sup 2+} and HMT had the highest aspect ratio, the largest surface roughness and the lowest band gap energy, which was beneficial to the efficiency of UV light utilization, photocatalytic degradation of estrone and H{sub 2}O{sub 2} generation.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Hydrogen Generation from Ammonia Borane and Water Through the Combustion Reactions with Mechanically Alloyed Al/Mg Powder

    Science.gov (United States)

    2014-08-11

    synthesis of ammonia -A ‘‘never ending story? " Angewandte...34 # && , (/ -%(/ &$’$) ) ! -( ( !( &" # ( %’ !&% # ’)( (% (" %’% (" ( & *%" # ’)( *! % + 3 HYDROGEN GENERATION FROM AMMONIA BORANE AND WATER THROUGH THE...FROM AMMONIA BORANE AND WATER THROUGH THE COMBUSTION REACTIONS WITH MECHANICALLY ALLOYED AL/MG POWDER by DANIEL RODRIGUEZ THESIS Presented to

  14. 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

  15. 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.

  16. A Highly Efficient and Self-Stabilizing Metallic-Glass Catalyst for Electrochemical Hydrogen Generation.

    Science.gov (United States)

    Hu, Yuan Chao; Wang, Yi Zhi; Su, Rui; Cao, Cheng Rong; Li, Fan; Sun, Chun Wen; Yang, Yong; Guan, Peng Fei; Ding, Da Wei; Wang, Zhong Lin; Wang, Wei Hua

    2016-12-01

    A multicomponent metallic glass (MG) with highly efficient and anomalous durability for catalyzing water splitting is reported. The outstanding performance of the MG catalyst contributed by self-optimized active sites originates from the intrinsic chemical heterogeneity and selective dealloying on the disordered surface; thus, a new mechanism for improving the durability of catalysts is uncovered.

  17. 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)

  18. 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.

  19. 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.

  20. Gain generator optimization for hydrogen fluoride overtone and fundamental chemical lasers

    Science.gov (United States)

    Duncan, William A.; Patterson, Stanley P.; Graves, Bruce R.; Sollee, Jeffrey L.; Yonehara, Gordon N.; Dering, John P.

    1993-06-01

    The hydrogen fluoride (HF) chemical laser is the baseline concept for SDIO space based laser (SBL) weapons systems. Ground based tests at power levels appropriate for this application have been demonstrated. Because the brightness of a laser beam projected to the far field is inversely proportional to the square of the wavelength, shorter wavelengths are desirable to enhance brightness on target. Development of the HF overtone chemical laser ((lambda) equals 1.3 - 1.4 micrometers ) as a growth technology for SBL applications has proceeded rapidly during the past several years. This paper reviews the parametric characterization and optimization of the Hypersonic, Low-Temperature (HYLTE) nozzle concept for HF overtone and HF fundamental performance. The experiments utilize advanced multilayer dielectric coatings on uncooled silicon substrates. The experimental results reported include laser power, small signal gain, mode footprint, and spectral content. The design of a multiple nozzle HYLTE module as a building block to an advanced high power HF chemical laser device is presented. Design philosophy emphasizes traceability from an intermediate size linear module to a full scale cylindrical gain generator for SBL applications. The key issues addressed are power scalability, fabricability, regenerative cooling capability, and thermal/structural performance.

  1. 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

  2. Design and Control of Integrated Systems for Hydrogen Production and Power Generation

    Science.gov (United States)

    Georgis, Dimitrios

    Growing concerns on CO2 emissions have led to the development of highly efficient power plants. Options for increased energy efficiencies include alternative energy conversion pathways, energy integration and process intensification. Solid oxide fuel cells (SOFC) constitute a promising alternative for power generation since they convert the chemical energy electrochemically directly to electricity. Their high operating temperature shows potential for energy integration with energy intensive units (e.g. steam reforming reactors). Although energy integration is an essential tool for increased efficiencies, it leads to highly complex process schemes with rich dynamic behavior, which are challenging to control. Furthermore, the use of process intensification for increased energy efficiency imposes an additional control challenge. This dissertation identifies and proposes solutions on design, operational and control challenges of integrated systems for hydrogen production and power generation. Initially, a study on energy integrated SOFC systems is presented. Design alternatives are identified, control strategies are proposed for each alternative and their validity is evaluated under different operational scenarios. The operational range of the proposed control strategies is also analyzed. Next, thermal management of water gas shift membrane reactors, which are a typical application of process intensification, is considered. Design and operational objectives are identified and a control strategy is proposed employing advanced control algorithms. The performance of the proposed control strategy is evaluated and compared with classical control strategies. Finally SOFC systems for combined heat and power applications are considered. Multiple recycle loops are placed to increase design flexibility. Different operational objectives are identified and a nonlinear optimization problem is formulated. Optimal designs are obtained and their features are discussed and compared

  3. 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.

  4. Polymer membrane based electrolytic cell and process for the direct generation of hydrogen peroxide in liquid streams

    Science.gov (United States)

    White, James H. (Inventor); Schwartz, Michael (Inventor); Sammells, Anthony F. (Inventor)

    1997-01-01

    An electrolytic cell for generating hydrogen peroxide is provided including a cathode containing a catalyst for the reduction of oxygen, and an anode containing a catalyst for the oxidation of water. A polymer membrane, semipermeable to either protons or hydroxide ions is also included and has a first face interfacing to the cathode and a second face interfacing to the anode so that when a stream of water containing dissolved oxygen or oxygen bubbles is passed over the cathode and a stream of water is passed over the anode, and an electric current is passed between the anode and the cathode, hydrogen peroxide is generated at the cathode and oxygen is generated at the anode.

  5. Hydrogen generation from methylamine using silicon carbide nanotubes as a dehydrogenation catalyst: a density functional theory study.

    Science.gov (United States)

    Esrafili, Mehdi D; Nurazar, Roghaye

    2015-02-01

    The adsorption and decomposition of methylamine on the surface of a pristine silicon-carbide nanotube (SiCNT) are investigated by density functional theory calculations. The adsorption energies of possible stable configurations and the activation energies for possible elementary reactions involved are obtained in the present study. The most favorable reaction channel that generates a hydrogen cyanide molecule and four hydrogen atoms is slightly endothermic; the energy barrier for the decomposition of the CH3NH2 molecule is about 45 kcal/mol. Since the activation energy for the side reaction that generates CH3 and NH2 fragments is relatively high, the generation of side products may be depressed by decreasing the temperature.

  6. 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

  7. 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

  8. 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 th...

  9. 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.

  10. A Convenient Hydrogenation Method for the Synthesis of Metallo-mesoporphyrin IX Dimethyl Esters via Self-catalyzed CoCI2-NaBH4 Reagent System

    Institute of Scientific and Technical Information of China (English)

    徐士超; 胡炳成; 胡田菁; 王欢; 黄修有; 娄兴焜; 刘祖亮

    2012-01-01

    A convenient protocol has been developed for the hydrogenation of metallo-protoporphyrin IX dimethyl esters (MPPDMEs) to their mesoporphyrin analogues using CoC12-NaBH4 reagent system. Metallo-porphyrin complexes were found to perform as self-catalysts in this procedure. This method provides several advantages such as safe and simple procedure, short reaction time, high yields and low cost.

  11. 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.

  12. 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.

  13. Photoelectrocatalytic hydrogen generation and simultaneous degradation of organic pollutant via CdSe/TiO{sub 2} nanotube arrays

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wenchao [Department of Chemistry, Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Normal University, Shanghai 200234 (China); Li, Fang [Department of Chemistry, Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Normal University, Shanghai 200234 (China); Department of Mechanical Engineering, The University of Hong Kong, Pok Fu Lam, Hong Kong (China); Zhang, Dieqing [Department of Chemistry, Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Normal University, Shanghai 200234 (China); Leung, Dennis Y.C., E-mail: ycleung@hku.hk [Department of Mechanical Engineering, The University of Hong Kong, Pok Fu Lam, Hong Kong (China); Li, Guisheng, E-mail: liguisheng@shnu.edu.cn [Department of Chemistry, Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Normal University, Shanghai 200234 (China)

    2016-01-30

    Graphical abstract: A highly efficient CdSe/TiO{sub 2} nanotube arrays photoanode was explored via the electrodeposition with ion-exchange method for photoelectrocatalytic hydrogen evolution and simultaneous degradation of organic pollutant under visible light irradiation. - Highlights: • CdSe nanoparticles enhanced TiO{sub 2} nanotube arrays electrode was prepared by an electrodeposition with ion-exchange method. • CdSe nanoparticles were strongly bonded on the pore walls of TiO{sub 2} nanotube arrays, with the formation of CdSe–TiO{sub 2} heterojunctions. • Such CdSe/TiO{sub 2} nanotubes arrays, acting as photoanode, exhibited high efficiency for both generation of hydrogen and degradation of MO in photoelectrocatalysis reaction system under visible-light irradiation. - Abstract: CdSe nanoparticles enhanced TiO{sub 2} nanotube arrays electrodes (CdSe/TNTAs) were explored as the photoanode for driving the photoelectrocatalytic (PEC) generation of hydrogen and simultaneous degradation of organic pollutants in a PEC system. The evolution hydrogen and the simultaneous degradation of organic pollutants were performed in an electrolytic cell (three electrodes system) under visible-light (λ > 400 nm). Such CdSe/TiO{sub 2} based PEC system exhibited both high efficiency of hydrogen generation and effective oxidation of methyl orange (MO). Such high PEC performance of CdSe/TNTAs was attributed to the high dispersity of CdSe nanoparticles on both outside and inside of the pore walls of TiO{sub 2} nanotube arrays, the strong combination and heterojunctions between CdSe and TiO{sub 2} through Cd−O bonds via electrodeposition with ion-exchange method.

  14. A hydrogen peroxide-generating agent, 6-formylpterin, enhances heat-induced apoptosis.

    Science.gov (United States)

    Wada, S; Cui, Z-G; Kondo, T; Zhao, Q-L; Ogawa, R; Shoji, M; Arai, T; Makino, K; Furuta, I

    2005-05-01

    The enhancement of heat-induced apoptosis by 6-formylpterin, an intra-cellular generator of hydrogen peroxide (H2O2), was examined in human myelomonocytic lymphoma U937 cells. The cells were treated with either 6-formylpterin alone at a nontoxic concentration of 300 microM (37 degrees C), heat shock (44 degrees C per 20 min) alone or a combination of the two, then incubated at 37 degrees C for 6 h. Assessments of apoptosis, mitochondrial membrane potential and caspase-3 activation were performed by flow cytometry. Moreover, caspase-8 activation and changes in the intra-cellular Ca2+ concentration ([Ca2+]i) were examined. Bax, Bcl-2, Bcl-XL, Bid, cytochrome c and PKCd were detected by Western blotting. The induction of heat-induced apoptosis evaluated by morphological observation and DNA fragmentation were promoted by the addition of 6-formylpterin. Mitochondrial membrane potential was decreased and the activation of caspase-3 and -8 was enhanced in the cells treated with the combination. A decreased-expression of Bid was noted, although no significant changes in Bax, Bcl-2 and Bcl-XL expression were observed after the combined treatment. Furthermore, both the release of cytochrome c from mitochondria to cytosol and the translocation of PKCd from cytosol to mitochondria, which were induced by heat shock, were enhanced by the addition of 6-formylpterin. The number of cells with a higher [Ca2+]i was also increased by the addition of 6-formylpterin. These findings suggest that the increase in [Ca2+]i, the activation of the mitochondria-caspase dependent pathway and the translocation of PKCd to mitochondria play principal roles in the enhancement of heat-induced apoptosis by 6-FP.

  15. Efficiency and stability aspects of CdS photoanode for solar hydrogen generation technology

    Science.gov (United States)

    Pareek, Alka; Gopalakrishnan, Arthi; Borse, Pramod H.

    2016-10-01

    Photoelectrochemical (PEC) cell based technology is expected to be one of the easiest green technologies to harness and to convert available solar energy into hydrogen [1]. Among the known systems of GaAs, Si, GaP and CdS- Cadmium sulphide is one of the best suited PEC materials that display a balance between its efficiency and stability. It has capability to absorb the visible light photons (E∼1.5eV - 3eV), and displays the band- energetics that suits for water-splitting reaction (H2O→H2+O2), that ultimately is based on the electronic and optical structure of the sulphides. However, the photo-induced dissolution of CdS in an electrolyte during its photo-illumination in PEC cell is its major drawback [2]. Though arsenides and phosphides show higher efficiency however CdS exhibits significant stability. In contrast though TiO2/ ZnO show good stability but CdS displays good optical response towards visible light photons as compared null response of titanate like systems. This necessitates one to identify the practical way to inhibit the photocorrosion in case of CdS photoanodes which is mainly facilitated due to interaction of photogenerated holes with CdS lattice. In past, Pt/ RuO2/ Ru modified CdS surface were found to control the unwanted photocorrosion [3]. Commercially, usage of such materials is un-economic option for any technological usage. The present work discusses that with advent of present day new synthetic routes how the dynamics of photo generated holes and electrons can be controlled to improve the stability and efficiency of the sulphide photoanodes, which in turn shows an an improvement in the performance and stability of the PEC cell for desirable technological applications.

  16. 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.

  17. Optimization of efficiency and energy density of passive micro fuel cells and galvanic hydrogen generators

    OpenAIRE

    Hahn, Robert; Wagner,Stefan; Krumbholz, Steffen; Reichl, Herbert

    2008-01-01

    Submitted on behalf of EDA Publishing Association (http://irevues.inist.fr/handle/2042/16838); International audience; 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 improv...

  18. 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.

  19. Induction of Low-Level Hydrogen Peroxide Generation by Unbleached Cotton Nonwovens as Potential Wound Dressing Materials.

    Science.gov (United States)

    Edwards, J Vincent; Prevost, Nicolette T; Nam, Sunghyun; Hinchliffe, Doug; Condon, Brian; Yager, Dorne

    2017-03-06

    Greige cotton is an intact plant fiber. The cuticle and primary cell wall near the outer surface of the cotton fiber contains pectin, peroxidases, superoxide dismutase (SOD), and trace metals, which are associated with hydrogen peroxide (H₂O₂) generation during cotton fiber development. Traditionally, the processing of cotton into gauze involves scouring and bleaching processes that remove the components in the cuticle and primary cell wall. The use of unbleached, greige cotton fibers in dressings, has been relatively unexplored. We have recently determined that greige cotton can generate low levels of H₂O₂ (5-50 micromolar). Because this may provide advantages for the use of greige cotton-based wound dressings, we have begun to examine this in more detail. Both brown and white cotton varieties were examined in this study. Brown cotton was found to have a relatively higher hydrogen peroxide generation and demonstrated different capacities for H₂O₂ generation, varying from 1 to 35 micromolar. The H₂O₂ generation capacities of white and brown nonwoven greige cottons were also examined at different process stages with varying chronology and source parameters, from field to nonwoven fiber. The primary cell wall of nonwoven brown cotton appeared very intact, as observed by transmission electron microscopy, and possessed higher pectin levels. The levels of pectin, SOD, and polyphenolics, correlated with H₂O₂ generation.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. ASSESSMENT OF THE POTENTIAL FOR HYDROGEN GENERATION DURING GROUTING OPERATIONS IN THE R- AND P-REACTOR VESSELS

    Energy Technology Data Exchange (ETDEWEB)

    Wiersma, B.

    2009-12-29

    at a temperature of 80 C, the risk will again be very 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 0.32 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.

  6. 水杨酸正戊酯的催化合成研究%Synthesis of n-Amyl Salicylate Catalyzed by Sodium Hydrogen Sulfate

    Institute of Scientific and Technical Information of China (English)

    杨华; 马荣萱

    2009-01-01

    n-Amyl salicylate was synthesized from salicylic acid and n-pentanol using sodium hydrogen sulfate as catalyst. Factors influencing the ether yield,such as molar ratio of alcohol to acid,catalyst dosage,reaction time,water carrier dosage were discussed. Experimental results showed that sodium hydrogen sulfate was an excellent catalyst. The optimum synthetic conditions were as follows: molar ratio of salicylic acid to n-pentanol was 1∶1.5,catalyst dosage was 4.7% of mass of the reactants,using 10 mL of cyclohexane as water carrier,reaction temperature was 120~140℃ and reaction time was 4.5 h.Under above conditions, the yield of n-amyl salicylate achieved 93.3%.%以水杨酸和正戊醇为原料,用一水合硫酸氢钠催化合成水杨酸正戊酯.研究了酸醇摩尔比、催化剂用量、反应时间及带水剂用量等因素对酯收率的影响.结果表明,一水合硫酸氢钠是合成水杨酸正戊酯的良好催化剂.最佳反应条件如下:酸醇摩尔比为1∶1.5,催化剂用量为反应物总质量的4.7%,带水剂环己烷用量为10 mL,反应时间为4.5 h,反应温度为120~140℃.在此条件下,水杨酸正戊酯的收率可达93.3%.

  7. 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.

  8. 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.

  9. 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.

  10. Efficient photoelectrochemical hydrogen generation using heterostructures of Si and chemically exfoliated metallic MoS2.

    Science.gov (United States)

    Ding, Qi; Meng, Fei; English, Caroline R; Cabán-Acevedo, Miguel; Shearer, Melinda J; Liang, Dong; Daniel, Andrew S; Hamers, Robert J; Jin, Song

    2014-06-18

    We report the preparation and characterization of highly efficient and robust photocathodes based on heterostructures of chemically exfoliated metallic 1T-MoS2 and planar p-type Si for solar-driven hydrogen production. Photocurrents up to 17.6 mA/cm(2) at 0 V vs reversible hydrogen electrode were achieved under simulated 1 sun irradiation, and excellent stability was demonstrated over long-term operation. Electrochemical impedance spectroscopy revealed low charge-transfer resistances at the semiconductor/catalyst and catalyst/electrolyte interfaces, and surface photoresponse measurements also demonstrated slow carrier recombination dynamics and consequently efficient charge carrier separation, providing further evidence for the superior performance. Our results suggest that chemically exfoliated 1T-MoS2/Si heterostructures are promising earth-abundant alternatives to photocathodes based on noble metal catalysts for solar-driven hydrogen production.

  11. 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.

  12. Power generation in fuel cells using liquid methanol and hydrogen peroxide

    Science.gov (United States)

    Narayanan, Sekharipuram R. (Inventor); Valdez, Thomas I. (Inventor); Chun, William (Inventor)

    2002-01-01

    The invention is directed to an encapsulated fuel cell including a methanol source that feeds liquid methanol (CH.sub.3 OH) to an anode. The anode is electrical communication with a load that provides electrical power. The fuel cell also includes a hydrogen peroxide source that feeds liquid hydrogen peroxide (H.sub.2 O.sub.2) to the cathode. The cathode is also in communication with the electrical load. The anode and cathode are in contact with and separated by a proton-conducting polymer electrolyte membrane.

  13. ASSESSMENT OF THE POTENTIAL FOR HYDROGEN GENERATION DURING GROUTING OPERATIONS IN THE R AND P REACTOR VESSELS

    Energy Technology Data Exchange (ETDEWEB)

    Wiersma, B.

    2009-10-29

    The R- and P-reactor buildings were retired from service and are now being prepared for deactivation and decommissioning (D&D). D&D activities will consist primarily of immobilizing contaminated components and structures in a grout-like formulation. Aluminum corrodes very rapidly when it comes in contact with the alkaline grout materials and as a result produces hydrogen gas. To address this potential deflagration/explosion hazard, the Materials Science and Technology Directorate (MS&T) of the Savannah River National Laboratory (SRNL) has been requested to review and evaluate existing experimental and analytical studies of this issue to determine if any process constraints on the chemistry of the fill material and the fill operation are necessary. Various options exist for the type of grout material that may be used for D&D of the reactor vessels. The grout formulation options include ceramicrete (pH 6-8), low pH portland cement + silica fume grout (pH 10.4), or portland cement grout (pH 12.5). The assessment concluded that either ceramicrete or the silica fume grout may be used to safely grout the R- and P- reactor vessels. The risk of accumulation of a flammable mixture of hydrogen between the grout-air interface and the top of the reactor is very low. Conservative calculations estimate that either ceramicrete or the silica fume grout may be used to safely grout the R- and P- reactor vessels. The risk of accumulation of a flammable mixture of hydrogen between the grout-air interface and the top of the reactor is very 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. Grout temperatures less than 100 C should however, still provide an adequate safety margin for the pH 8 and pH 10.4 grout formulations. (2) Minimize the fill rate as much as

  14. Plasmonic ZnO/Ag embedded structures as collecting layers for photogenerating electrons in solar hydrogen generation photoelectrodes.

    Science.gov (United States)

    Chen, Hao Ming; Chen, Chih Kai; Tseng, Ming Lun; Wu, Pin Chieh; Chang, Chia Min; Cheng, Liang-Chien; Huang, Hsin Wei; Chan, Ting Shan; Huang, Ding-Wei; Liu, Ru-Shi; Tsai, Din Ping

    2013-09-09

    A new fabrication strategy in which Ag plasmonics are embedded in the interface between ZnO nanorods and a conducting substrate is experimentally demonstrated using a femtosecond-laser (fs-laser)-induced plasmonic ZnO/Ag photoelectrodes. This fs-laser fabrication technique can be applied to generate patternable plasmonic nanostructures for improving their effectiveness in hydrogen generation. Plasmonic ZnO/Ag nanostructure photoelectrodes show an increase in the photocurrent of a ZnO nanorod photoelectrodes by higher than 85% at 0.5 V. Both localized surface plasmon resonance in metal nanoparticles and plasmon polaritons propagating at the metal/semiconductor interface are available for improving the capture of sunlight and collecting charge carriers. Furthermore, in-situ X-ray absorption spectroscopy is performed to monitor the plasmonic-generating electromagnetic field upon the interface between ZnO/Ag nanostructures. This can reveal induced vacancies on the conduction band of ZnO, which allow effective separation of charge carriers and improves the efficiency of hydrogen generation. Plasmon-induced effects enhance the photoresponse simultaneously, by improving optical absorbance and facilitating the separation of charge carriers.

  15. Production of hydrogen by electron transfer catalysis using conventional and photochemical means

    Science.gov (United States)

    Rillema, D. P.

    1981-03-01

    Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

  16. Kinetics and mechanisms of the oxidation of alcohols and hydroxylamines by hydrogen peroxide, catalyzed by methyltrioxorhenium, MTO, and the oxygen binding properties of cobalt Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zauche, Timothy [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    Catalysis is a very interesting area of chemistry, which is currently developing at a rapid pace. A great deal of effort is being put forth by both industry and academia to make reactions faster and more productive. One method of accomplishing this is by the development of catalysts. Enzymes are an example of catalysts that are able to perform reactions on a very rapid time scale and also very specifically; a goal for every man-made catalyst. A kinetic study can also be carried out for a reaction to gain a better understanding of its mechanism and to determine what type of catalyst would assist the reaction. Kinetic studies can also help determine other factors, such as the shelf life of a chemical, or the optimum temperature for an industrial scale reaction. An area of catalysis being studied at this time is that of oxygenations. Life on this earth depends on the kinetic barriers for oxygen in its various forms. If it were not for these barriers, molecular oxygen, water, and the oxygenated materials in the land would be in a constant equilibrium. These same barriers must be overcome when performing oxygenation reactions on the laboratory or industrial scale. By performing kinetic studies and developing catalysts for these reactions, a large number of reactions can be made more economical, while making less unwanted byproducts. For this dissertation the activation by transition metal complexes of hydrogen peroxide or molecular oxygen coordination will be discussed.

  17. 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

  18. 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…

  19. Quantum Dot Superlattice Enabled Rational Design in Optoelectronics and Hydrogen Generation

    Science.gov (United States)

    2014-11-25

    Final 3. DATES COVERED (From - To) 22-April-2013 to 21-April-2014 4. TITLE AND SUBTITLE Quantum Dot Superlattice Enabled Rational Design...15. SUBJECT TERMS Quantum Dots , Optoelectronic Applications, Charge Transfer, Superlattices, Density Functional Theory, Coupling...FA2386-13-1-4074 “ Quantum Dot Superlattice Enabled Rational Design in Optoelectronics and Hydrogen Generation” April 21, 2014 PI and Co-PI

  20. 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)

  1. ASSESSMENT OF THE POTENTIAL FOR HYDROGEN GENERATION DURING DEACTIVATION AND DECOMMISSIONING OF REACTOR VESSELS AT THE SAVANNAH RIVER SITE

    Energy Technology Data Exchange (ETDEWEB)

    Wiersma, B.; Serrato, M.; Langton, C.

    2010-11-10

    The R- and P-reactor vessels at the Savannah River Site (SRS) are being prepared for deactivation and decommissioning (D&D). D&D activities will consist primarily of physically isolating and stabilizing the reactor vessel by filling it with a grout material. The reactor vessels contain aluminum alloy materials, which pose a concern in that aluminum corrodes rapidly when it comes in contact with the alkaline grout. A product of the corrosion reaction is hydrogen gas and therefore potential flammability issues were assessed. A model was developed to calculate the hydrogen generation rate as the reactor is being filled with the grout material. Three options existed for the type of grout material for D&D of the reactor vessels. The grout formulation options included ceramicrete (pH 6-8), a calcium aluminate sulfate (CAS) based cement (pH 10), or Portland cement grout (pH 12.4). Corrosion data for aluminum in concrete were utilized as input for the model. The calculations considered such factors as the surface area of the aluminum components, the open cross-sectional area of the reactor vessel, the rate at which the grout is added to the reactor vessel, and temperature. Given the hydrogen generation rate, the hydrogen concentration in the vapor space of the reactor vessel above the grout was calculated. This concentration was compared to the lower flammability limit for hydrogen. The assessment concluded that either ceramicrete or the CAS grout may be used to safely grout the P-reactor vessel. The risk of accumulation of a flammable mixture of hydrogen between the grout-air interface and the top of the reactor is very low. Portland cement grout, on the other hand, for the same range of process parameters did not provide a margin of safety against the accumulation of flammable gas in the reactor vessel during grouting operations in the P-reactor vessel. Therefore, it was recommended that this grout not be utilized for this task. On the other hand, the R-reactor vessel

  2. Does the MgO(100)-support facilitate the reaction of nitrogen and hydrogen molecules catalyzed by Zr2Pd2 clusters? A computational study.

    Science.gov (United States)

    Kuznetsov, Aleksey E; Musaev, Djamaladdin G

    2010-03-01

    Reactions of the "naked" and MgO(100) supported Zr(2)Pd(2) cluster with nitrogen and four hydrogen molecules were studied at the density functional level using the periodic slab approach (VASP). It was shown that adsorption of the Zr(2)Pd(2) cluster on the MgO(100) surface does not change its gas-phase geometry and electronic structure significantly. In spite of this the N(2) coordination to the MgO(100)-supported Zr(2)Pd(2) cluster, I/MgO, is found to be almost 30 kcal/mol less favorable than for the "naked" one. The addition of the first H(2) molecule to the resulting II/MgO, that is, II/MgO + H(2) --> IV/MgO reaction, proceeds with a relatively small, 9.0 kcal/mol, barrier and is exothermic by 8.3 kcal/mol. The same reaction for the "naked" Zr(2)Pd(2) cluster requires a slightly larger barrier (10.1 kcal/mol) and is highly exothermic (by 23.3 kcal/mol). The interaction of the H(2) molecule with the intermediate IV/MgO (i.e., the second H(2) molecule addition to II/MgO) requires larger energy barrier, 23.3 kcal/mol vs 8.8 kcal/mol for the "naked" cluster, and is exothermic by 20.5 kcal/mol (vs 18.2 kcal/mol reported for the "naked" Zr(2)Pd(2) cluster). The addition of the H(2) molecule to VI/MgO and VI (i.e., the third H(2) molecule addition to II/MgO and II, respectively) requires similar barriers, 12.0 versus 16.8 kcal/mol, respectively, but is highly exothermic for the supported cluster compared to the "naked" one, 13.6 versus 0.1 kcal/mol. The addition of the fourth H(2) molecule occurs with almost twice larger barrier for the "naked" cluster compared to the adsorbed species, 30.7 versus 15.9 kcal/mol. Furthermore, this reaction step is endothermic (by 11.4 kcal/mol) for the gas-phase cluster but exothermic by 7.8 kcal/mol for the adsorbed cluster. Dissociation of the formed hydrazine molecule from the on-surface complex X/MgO and the "naked" complex X requires 19.1 and 26.3 kcal/mol, respectively. Thus, the Zr(2)Pd(2) adsorption on the MgO(100) surface

  3. 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

  4. Silver quantum cluster (ag9 )-grafted graphitic carbon nitride nanosheets for photocatalytic hydrogen generation and dye degradation.

    Science.gov (United States)

    Sridharan, Kishore; Jang, Eunyong; Park, Jung Hyun; Kim, Jong-Ho; Lee, Jung-Ho; Park, Tae Joo

    2015-06-15

    We report the visible-light photocatalytic properties of a composite system consisting of silver quantum clusters [Ag9 (H2 MSA)7 ] (H2 MSA=mercaptosuccinic acid) embedded on graphitic carbon nitride nanosheets (AgQCs-GCN). The composites were prepared through a simple chemical route; their structural, chemical, morphological, and optical properties were characterized by using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, transmission electron microscopy, UV/Vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy. Embedment of [Ag9 (H2 MSA)7 ] on graphitic carbon nitride nanosheets (GCN) resulted in extended visible-light absorption through multiple single-electron transitions in Ag quantum clusters and an effective electronic structure for hydroxyl radical generation, which enabled increased activity in the photocatalytic degradation of methylene blue and methyl orange dye molecules compared with pristine GCN and silver nanoparticle-grafted GCN (AgNPs-GCN). Similarly, the amount of hydrogen generated by using AgQCs-GCN was 1.7 times higher than pristine GCN. However, the rate of hydrogen generated using AgQCs-GCN was slightly less than that of AgNPs-GCN because of surface hydroxyl radical formation. The plausible photocatalytic processes are discussed in detail.

  5. 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.

  6. 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).

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Theoretical study of piezoelectrochemical reactions in molecular compression chambers: In-situ generation of molecular hydrogen

    Science.gov (United States)

    Pichierri, Fabio

    2016-09-01

    Nitrogen-containing molecular compression chambers (MCCs) undergo stepwise protonation followed by a 2-electron reduction step which affords molecular hydrogen in situ. This piezoelectrochemical reaction is favored by the high compression that characterizes the molecular skeleton of MCC and its fluorinated analogue. Besides H2, the MCCs are also capable of trapping molecular fluorine and the small monoatomic gases helium and neon. A topological analysis of the electronic charge density reveals the presence of closed-shell interactions between hosts and guests.

  12. A modelling evaluation of an ammonia-fuelled microchannel reformer for hydrogen generation

    OpenAIRE

    Chiuta, Steven; Everson, Raymond C.; Neomagus, Hein W.J.P.; Le Grange, Louis A.; Bessarabov, Dmitri G.

    2014-01-01

    Hydrogen production from an ammonia-fuelled microchannel reactor is simulated in a three-dimensional (3D) model implemented via Comsol Multiphysics™. The work described in this paper endeavours to obtain a mathematical framework that provides an understanding of reaction-coupled transport phenomena within the microchannel reactor. The transport processes and reactor performance are elucidated in terms of velocity, temperature, and species concentration distributions, as well as local reaction...

  13. 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.

  14. Renewable Bio-solar Hydrogen Production from Robust Oxygenic Phototrophs: The Second Generation

    Science.gov (United States)

    2015-01-22

    of Biotechnology , 2013. 166: p. 65– 75. 4) McNeely K., Kumaraswamy G.K., et al. (2014). Metabolic Switching of Central Carbon Metabolism in...Response to Nitrate: Application to Autofermentative Hydrogen Production in Cyanobacteria. Journal of Biotechnology , 182-183, 83-91. 5) Smith, PF, Kaplan...Waksman Institute of Microbiology and the Dept of Chemistry & Chem. Biology, Rutgers The State University of New Jersey, Piscataway, NJ 5. Telephone

  15. 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.

  16. 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.

  17. Sequential generation of hydrogen and methane from glutamic acid through combined photo-fermentation and methanogenesis.

    Science.gov (United States)

    Xia, Ao; Cheng, Jun; Lin, Richen; Liu, Jianzhong; Zhou, Junhu; Cen, Kefa

    2013-03-01

    Glutamic acid can hardly produce hydrogen via dark- or photo-fermentation without pretreatment. In this study, a novel process of acidogenic pretreatment with bacteria and zeolite treatment for NH4(+) removal was proposed to use glutamic acid as feedstock in photo-fermentation for efficient hydrogen production. Glutamic acid pretreated with acidogenic bacteria produces soluble metabolite products. After zeolite treatment, the acidulated solution, which mainly contains acetate, butyrate, and NH4(+), shows a decrease in NH4(+) concentration from 36.7mM to 3.2mM (NH4(+) removal efficiency of 91.1%). After NH4(+) removal, the treated solution is incubated with photosynthetic bacteria, exhibiting a maximum hydrogen yield of 292.9mL/g(-glutamic acid) during photo-fermentation. The residual solution from photo-fermentation is reused by methanogenic bacteria to produce a maximum methane yield of 102.7mL/g. The heating value conversion efficiency from glutamic acid to gas fuel significantly increases from 18.9% during photo-fermentation to 40.9% in the combined photo-fermentation and methanogenesis process.

  18. 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.

  19. Efficient and Stable MoS2 /CdSe/NiO Photocathode for Photoelectrochemical Hydrogen Generation from Water.

    Science.gov (United States)

    Dong, Yuming; Chen, Yanmei; Jiang, Pingping; Wang, Guangli; Wu, Xiuming; Wu, Ruixian; Zhang, Chi

    2015-08-01

    A novel CdSe/NiO heteroarchitecture was designed, prepared, and used as a photocathode for hydrogen generation from water. The composite films were structurally, optically, and photoelectrochemically characterized. The deposition of CdSe on the NiO film enhanced light harvesting in the visible-light region and photoelectrochemical properties. Moreover, the CdSe/NiO photoelectrode showed superior stability both in nitrogen-saturated and air-saturated neutral environments. The CdSe/NiO photoelectrode after MoS2 modification retained the stability of the CdSe/NiO electrode and exhibited higher photocatalytic and photoelectrochemical performances than the unmodified CdSe/NiO electrode. In pH 6 buffer solution, an average hydrogen-evolution rate of 0.52 μmol h(-1)  cm(-2) at -0.131 V (versus reversible hydrogen electrode, RHE) was achieved on a MoS2 /CdSe/NiO photocathode, with almost 100 % faradaic efficiency.

  20. 针铁矿催化过氧化氢降解PCB28%Degradation of PCB28 by goethite-catalyzed hydrogen peroxide

    Institute of Scientific and Technical Information of China (English)

    林志荣; 赵玲; 董元华; 徐建强

    2011-01-01

    Using goethite as a catalyst,the degradation of PCB28 was studied in the heterogeneous Fenton system containing goethite and hydrogen peroxide (H2O2).The dosage effect of goethite and H2O2 and the pH of the system on the degradation efficiency of PCB28 were also discussed.Moreover,the degradation mechanism of PCB28 in the heterogeneous Fenton system was discovered.Results showed that PCB28 was significantly degraded in the heterogeneous Fenton system.The degradation efficiency of PCB28 increased with the increaseing dosage of goethite and H2O2.The degradation efficiency of PCB28 was affected by the pH of the system,with the order of pH=3pH=8pH=5pH=7pH=9.No degradation of PCB28 was observed after methanol as a quenching reagent of the hydroxyl radicals was added into the heterogeneous Fenton system,indicating that the hydroxyl radicals were the reactive species during the degradation of PCB28.Few iron ions (Fe) were detected in the process of the reaction,which further indicated that PCB28 was directly degraded on the surface of goethite rather than by the aqueous Fenton system consisted of the soluble Fe from α-FeOOH.%以针铁矿(α-FeOOH)为催化剂,在针铁矿与H2O2组成的非均相Fenton体系内对PCB28的降解进行了研究,讨论了针铁矿、H2O2浓度和体系pH对PCB28降解率的影响,并初步揭示了PCB28的降解机理.结果表明,PCB28在非均相Fenton体系中能发生明显的降解作用.PCB28的降解率随H2O2和针铁矿初始浓度增加而显著增加.pH对PCB28降解率的影响表现为pH=3〉pH=8〉pH=5〉pH=7〉pH=9.在加入自由基猝灭剂甲醇后,PCB28基本不发生降解作用,表明反应的主要活性物质是羟基自由基.在反应过程中只溶出少量的铁离子,进一步表明降解反应是直接发生在FeOOH的表面,而非通过FeOOH溶出的铁离子组成均相Fenton体系降解PCB28.

  1. MHD-, ships-, jet engine unit consisting of electrochemical cells producing hydrogen, magneto-caloric hydrogen liquefier, liquid hydrogen-cooled high temperature superconductor-, MHD-, jet engine, liquid hydrogen internal combustion engine as high temperature-, superconductor-, generator-drive. High temperature superconductor coil and permanent magnet superconductor hollow cylinder as battery. MHD-Schiffs-Strahltriebwerks-Aggregat bestehend aus Wasserstoff-produzierenden elektrochemischen Solarzellen, magnetokalorischem Wasserstoffverfluessiger, Fluessigwasserstoff gekuehltem Hochtemperatur-Supraleiter-MHD-Strahltriebwerk, Fluessigwasserstoff-Verbrennungsmotor als Hochtemperatur-Supraleiter-Generator-Antrieb, Hochtemperatur-Supraleiter-Spule und permanentmagnetischem Supraleiter-Hohlzylinder als Akku

    Energy Technology Data Exchange (ETDEWEB)

    Berling, E.

    1991-05-02

    MHD-, ships-, jet engine-unit consisting of electrochemical cells producing hydrogen, magneto-caloric hydrogen liquifier, liquid hydrogen-cooled high temperature superconductor-, MHD-, jet engine, liquid hydrogen internal combustion engine as high temperature-, superconductor-, generator-drive. High temperature superconductor coil and permanent magnet superconductor hollow cylinder as battery. Ships water jet engines with magneto hydrodynamic (MHD) low temperature superconductor drive are known. The invention of the ceramic high temperature superconductor MHD drive, which is cooled with liquid hydrogen. The hydrogen is obtained electro-chemically directly from seawater, and is liquified magneto-calorically. The high temperature superconductor elements of the engine, liquifier, generator, storage coil, permanent magnet hollow cylinder store are coupled by a common liquid hydrogen cooling circuit. The internal combustion engine driving the generator is fuelled by the same liquid hydrogen by which the high temperature superconductor elements are cooled.

  2. 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.

  3. 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.

  4. On-board hydrogen generation for transport applications: the HotSpot™ methanol processor

    Science.gov (United States)

    Edwards, Neil; Ellis, Suzanne R.; Frost, Jonathan C.; Golunski, Stanislaw E.; van Keulen, Arjan N. J.; Lindewald, Nicklas G.; Reinkingh, Jessica G.

    In the absence of a hydrogen infrastructure, development of effective on-board fuel processors is likely to be critical to the commercialisation of fuel-cell cars. The HotSpot™ reactor converts methanol, water and air in a single compact catalyst bed into a reformate containing mainly CO2 and hydrogen (and unreacted nitrogen). The process occurs by a combination of exothermic partial oxidation and endothermic steam reforming of methanol, to produce 750 l of hydrogen per hour from a 245-cm3 reactor. The relative contribution of each reaction can be tuned to match the system requirements at a given time. Scale-up is achieved by the parallel combination of the required number of individual HotSpot reactors, which are fed from a central manifold. Using this modular design, the start-up and transient characteristics of a large fuel-processor are identical to that of a single reactor. When vaporised liquid feed and air are introduced into cold reactors, 100% output is achieved in 50 s; subsequent changes in throughput result in instantaneous changes in output. Surplus energy within the fuel-cell powertrain can be directed to the manifold, where it can be used to vaporise the liquid feeds and so promote steam reforming, resulting in high system efficiency. The small amount of CO that is produced by the HotSpot reactions is attenuated to <10 ppm by a catalytic clean-up unit. The HotSpot concept and CO clean-up strategy are not limited to the processing of methanol, but are being applied to other organic fuels.

  5. Compact Cryogenic Source of Periodic Hydrogen and Argon Droplet Beams for Intense Laser-Plasma Generation

    CERN Document Server

    Fraga, R A Costa; Kühnel, M; Hochhaus, D C; Schottelius, A; Polz, J; Kaluza, M C; Neumayer, P; Grisenti, R E

    2011-01-01

    We present a cryogenic source of periodic streams of micrometer-sized hydrogen (H2) and argon (Ar) droplets as ideal mass-limited target systems for fundamental intense laser-driven plasma applications. The highly compact design combined with a high temporal and spatial droplet stability makes our injector ideally suited for experiments using state-of-the-art low-repetition rate high-power lasers, in which a precise synchronization between the laser pulses and the droplets is mandatory. We demonstrate this explicitly by irradiating Ar droplets with pulses from a Petawatt laser.

  6. Compact cryogenic source of periodic hydrogen and argon droplet beams for relativistic laser-plasma generation

    Energy Technology Data Exchange (ETDEWEB)

    Fraga, R. A. Costa; Kalinin, A.; Kuehnel, M.; Schottelius, A. [Institut fuer Kernphysik, J. W. Goethe-Universitaet, Max-von-Laue-Str. 1, 60438 Frankfurt am Main (Germany); Hochhaus, D. C.; Neumayer, P. [EMMI Extreme Matter Institute and Research Division, GSI Helmholtzzentrum fuer Schwerionenforschung, Planckstr. 1, 64291 Darmstadt (Germany); FIAS Frankfurt Institute for Advanced Studies, J. W. Goethe-Universitaet, Ruth-Moufang-Str. 1, 60438 Frankfurt am Main (Germany); Polz, J. [Institut fuer Optik und Quantenelektronik, Max-Wien-Platz 1, 07743 Jena (Germany); Kaluza, M. C. [Institut fuer Optik und Quantenelektronik, Max-Wien-Platz 1, 07743 Jena (Germany); Helmholtz-Institut Jena, Froebelstieg 3, 07743 Jena (Germany); Grisenti, R. E. [Institut fuer Kernphysik, J. W. Goethe-Universitaet, Max-von-Laue-Str. 1, 60438 Frankfurt am Main (Germany); GSI Helmholtzzentrum fuer Schwerionenforschung, Planckstr. 1, 64291 Darmstadt (Germany)

    2012-02-15

    We present a cryogenic source of periodic streams of micrometer-sized hydrogen and argon droplets as ideal mass-limited target systems for fundamental intense laser-driven plasma applications. The highly compact design combined with a high temporal and spatial droplet stability makes our injector ideally suited for experiments using state-of-the-art high-power lasers in which a precise synchronization between the laser pulses and the droplets is mandatory. We show this by irradiating argon droplets with multi-terawatt pulses.

  7. 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.

  8. Hydrogen generation from 2,2,4-trimethyl pentane reforming over molybdenum carbide at low steam-to-carbon ratios

    Science.gov (United States)

    Cheekatamarla, Praveen K.; Thomson, William J.

    Because of the need for an efficient and inexpensive reforming catalyst, the objective of this work is to determine the feasibility of employing Mo 2C catalyst for the steam reforming and oxy-steam reforming of the higher hydrocarbons typical of transportation fuels such as gasoline. It is shown that bulk Mo 2C catalysts can successfully reform 2,2,4-trimethyl pentane (isooctane) to generate H 2, CO and CO 2 at very low steam/carbon ratios, without coke formation, eliminating the need for pre-reforming. Maximum hydrogen generation was observed at a S/C ratio of 1.3 and 1000 °C during SR reactions and S/C of 0.71, O 2/C of 0.12 at 900 °C during oxidative steam reforming reactions.

  9. 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.

  10. Generation of Useful Hydrocarbons and Hydrogen during Photocatalytic Decomposition of Acetic Acid on CuO/Rutile Photocatalysts

    Directory of Open Access Journals (Sweden)

    Sylwia Mozia

    2009-01-01

    Full Text Available The presented studies have focused on a photocatalytic generation of useful hydrocarbons, mainly methane and ethane, from acetic acid under N2 atmosphere. CuO-loaded rutile, as well as unmodified rutile and anatase-phase TiO2 photocatalysts were applied in the experiments. The efficiency of the catalysts towards methane generation changed in the following order: Cu-TiO2 (10% Cu > crude TiO2≈Cu-TiO2 (20% Cu > Cu-TiO2 (5% Cu > rutile. The amount of CH4 produced in the presence of the catalyst containing 10 wt% of Cu was higher for ca. 33% than in case of pure rutile. The concentration of ethane was 14–16 times lower than the amount of methane, regardless of the catalyst used. Low concentrations of hydrogen were also detected in the gaseous mixtures. After 5 hours of the process conducted with the catalyst containing 5–20 wt% of Cu the concentration of hydrogen amounted to 0.06–0.14 vol.%, respectively.

  11. Method and apparatus for electrokinetic co-generation of hydrogen and electric power from liquid water microjets

    Energy Technology Data Exchange (ETDEWEB)

    Saykally, Richard J; Duffin, Andrew M; Wilson, Kevin R; Rude, Bruce S

    2013-02-12

    A method and apparatus for producing both a gas and electrical power from a flowing liquid, the method comprising: a) providing a source liquid containing ions that when neutralized form a gas; b) providing a velocity to the source liquid relative to a solid material to form a charged liquid microjet, which subsequently breaks up into a droplet spay, the solid material forming a liquid-solid interface; and c) supplying electrons to the charged liquid by contacting a spray stream of the charged liquid with an electron source. In one embodiment, where the liquid is water, hydrogen gas is formed and a streaming current is generated. The apparatus comprises a source of pressurized liquid, a microjet nozzle, a conduit for delivering said liquid to said microjet nozzle, and a conductive metal target sufficiently spaced from said nozzle such that the jet stream produced by said microjet is discontinuous at said target. In one arrangement, with the metal nozzle and target electrically connected to ground, both hydrogen gas and a streaming current are generated at the target as it is impinged by the streaming, liquid spray microjet.

  12. Determination of photo conversion efficiency of nanotubular titanium oxide photo-electrochemical cell for solar hydrogen generation

    Science.gov (United States)

    Raja, K. S.; Mahajan, V. K.; Misra, M.

    Anodized and annealed titanium oxide nanotubes show enhanced photo activity and can be used as photo anodes for water electrolysis in hydrogen generation. Application of an external potential to the photo anode is required for enhancement of the photocurrent. This additional electrical energy input complicates the photo conversion efficiency calculation. In this investigation, the photo-electrochemical behavior of anodized titanium oxide nanotubular arrays have been characterized in various electrolytes. Increase in the applied potential increased the photocurrent under illumination with visible light. A simple experimental method for calculating the photo conversion efficiency has been proposed. According to this method, the potential difference between the photo anode and cathode is measured with and without light illumination. The product of the photocurrent and the increase in potential due to light irradiation is considered as the net power output. The photocurrent and the conversion efficiency increased with increase in the pH of the electrolyte. TiO 2 nanotubular arrays annealed at 350 °C for 6 h in nitrogen atmosphere showed a maximum photo conversion efficiency of ∼4% in 1 M KOH electrolyte and ∼3% in 3.5 wt.% sodium chloride solution. The results indicate that nanotubular TiO 2 can be potentially used for the photo electrolysis of seawater to generate hydrogen.

  13. A novel mechanism of formaldehyde neurotoxicity: inhibition of hydrogen sulfide generation by promoting overproduction of nitric oxide.

    Directory of Open Access Journals (Sweden)

    Xiao-Qing Tang

    Full Text Available BACKGROUND: Formaldehyde (FA induces neurotoxicity by overproduction of intracellular reactive oxygen species (ROS. Increasing studies have shown that hydrogen sulfide (H(2S, an endogenous gastransmitter, protects nerve cells against oxidative stress by its antioxidant effect. It has been shown that overproduction of nitric oxide (NO inhibits the activity of cystathionine-beta-synthase (CBS, the predominant H(2S-generating enzyme in the central nervous system. OBJECTIVE: We hypothesize that FA-caused neurotoxicity involves the deficiency of this endogenous protective antioxidant gas, which results from excessive generation of NO. The aim of this study is to evaluate whether FA disturbs H(2S synthesis in PC12 cells, and whether this disturbance is associated with overproduction of NO. PRINCIPAL FINDINGS: We showed that exposure of PC12 cells to FA causes reduction of viability, inhibition of CBS expression, decrease of endogenous H(2S production, and NO production. CBS silencing deteriorates FA-induced decreases in endogenous H(2S generation, neurotoxicity, and intracellular ROS accumulation in PC12 cells; while ADMA, a specific inhibitor of NOS significantly attenuates FA-induced decreases in endogenous H(2S generation, neurotoxicity, and intracellular ROS accumulation in PC12 cells. CONCLUSION/SIGNIFICANCE: Our data indicate that FA induces neurotoxicity by inhibiting the generation of H(2S through excess of NO and suggest that strategies to manipulate endogenous H(2S could open a suitable novel therapeutic avenue for FA-induced neurotoxicity.

  14. 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.

  15. 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

  16. Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution

    Science.gov (United States)

    Park, Sunghak; Chang, Woo Je; Lee, Chan Woo; Park, Sangbaek; Ahn, Hyo-Yong; Nam, Ki Tae

    2017-01-01

    The solar-driven splitting of hydrohalic acids (HX) is an important and fast growing research direction for H2 production. In addition to the hydrogen, the resulting chemicals (X2/X3-) can be used to propagate a continuous process in a closed cycle and are themselves useful products. Here we present a strategy for photocatalytic hydrogen iodide (HI) splitting using methylammonium lead iodide (MAPbI3) in an effort to develop a cost-effective and easily scalable process. Considering that MAPbI3 is a water-soluble ionic compound, we exploit the dynamic equilibrium of the dissolution and precipitation of MAPbI3 in saturated aqueous solutions. The I- and H+ concentrations of the aqueous solution are determined to be the critical parameters for the stabilization of the tetragonal MAPbI3 phase. Stable and efficient H2 production under visible light irradiation was demonstrated. The solar HI splitting efficiency of MAPbI3 was 0.81% when using Pt as a cocatalyst.

  17. Photo-electrochemical hydrogen generation using band-gap modified nanotubular titanium oxide in solar light

    Science.gov (United States)

    Raja, K. S.; Misra, M.; Mahajan, V. K.; Gandhi, T.; Pillai, P.; Mohapatra, S. K.

    Anodization of Ti in acidified fluoride solution results in an ordered nanotubular titanium oxide surface. In this study, vertically oriented arrays of TiO 2 nanotubes were prepared by incorporating nitrate and phosphate species during the anodization process. These nanotubes were annealed at 650 °C in a carbonaceous atmosphere using a chemical vapor deposition (CVD) furnace for a brief period. The carbon-modified nanotubular TiO 2 produced a photo-current density of more than 2.75 mA cm -2 at 0.2 V Ag/AgCl under solar light illumination. This photo-current density corresponds to a hydrogen evolution rate of about 11 l h -1 using a photo-anode of 1 m 2 area. The enhanced hydrogen evolution behavior of carbon-modified nanotubular TiO 2 is highly reproducible and sustainable for long duration. Annealed (at 350 °C in nitrogen atmosphere) TiO 2 nanotubes showed improved photo-activity as compared to the as-anodized or thermally oxidized TiO 2 photo-anodes.

  18. 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.

  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. 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.

  1. 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...... vapour diffused by Sterinis((R)) against MRSA in two experimental hospital settings and in two field trials. Dipslides were used for MRSA detection and quantification before and after using the Sterinis disinfection process. In the first experimental hospital setting, four epidemic MRSA strains were...... placed at five locations and left for one week. All strains survived the week but not the disinfection process. In field trial one 14 upholstered chairs from a department with many MRSA positive patients were left for one month in a closed room prior to disinfection. MRSA was found on the upholstery...

  2. Dark Photocatalysis: Storage of Solar Energy in Carbon Nitride for Time-Delayed Hydrogen Generation.

    Science.gov (United States)

    Lau, Vincent Wing-Hei; Klose, Daniel; Kasap, Hatice; Podjaski, Filip; Pignié, Marie-Claire; Reisner, Erwin; Jeschke, Gunnar; Lotsch, Bettina V

    2017-01-09

    While natural photosynthesis serves as the model system for efficient charge separation and decoupling of redox reactions, bio-inspired artificial systems typically lack applicability owing to synthetic challenges and structural complexity. We present herein a simple and inexpensive system that, under solar irradiation, forms highly reductive radicals in the presence of an electron donor, with lifetimes exceeding the diurnal cycle. This radical species is formed within a cyanamide-functionalized polymeric network of heptazine units and can give off its trapped electrons in the dark to yield H2 , triggered by a co-catalyst, thus enabling the temporal decoupling of the light and dark reactions of photocatalytic hydrogen production through the radical's longevity. The system introduced here thus demonstrates a new approach for storing sunlight as long-lived radicals, and provides the structural basis for designing photocatalysts with long-lived photo-induced states.

  3. 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)

  4. Studies in hydride generation atomic fluorescence determination of selenium and tellurium. Part 1 — self interference effect in hydrogen telluride generation and the effect of KI

    Science.gov (United States)

    D'Ulivo, A.; Marcucci, K.; Bramanti, E.; Lampugnani, L.; Zamboni, R.

    2000-08-01

    The effects of tetrahydroborate (0.02-1%) and iodide (0-3 M) were investigated in determination of tellurium and selenium by hydride generation atomic fluorescence spectrometry. The effect of tetrahydroborate and iodide concentration were tested on the shape of calibration curves in concentration range of 1-1000 ng ml -1 analyte. Reductant deficiency resulted in a moderate sensitivity depression for tellurium but dramatically reduced the useful dynamic range down to 50 ng ml -1. On the contrary, selenium calibration curves retained a linear character even under conditions generating strong sensitivity depression. Curvature and rollover of tellurium calibration curves has been addressed to a self-interference effect caused by the formation of finely dispersed elemental tellurium. Iodide ions were found to have beneficial or no negative effects in the hydrogen telluride generation. Addition of iodide on-line to the sample has been proved effective in the control of the self-interference effect and allows to work in mild reaction conditions. Moreover, it allows a good control of Cu(II) interference and eliminates Ni(II) and Co(II) interferences. The method has been successfully applied to determination of tellurium in copper and lead ores certified reference materials.

  5. 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.

  6. Effect of combined slow pyrolysis and steam gasification of sugarcane bagasse on hydrogen generation

    Energy Technology Data Exchange (ETDEWEB)

    Parthasarathy, Prakash; Narayanan, Sheeba [National Institute of Technology, Tamil Nadu (India)

    2015-11-15

    The present work aims at improving the generation of H2 from sugarcane bagasse in steam gasification process by incorporating slow pyrolysis technique. As a bench scale study, slow pyrolysis of sugarcane bagasse is performed at various pyrolysis temperature (350, 400, 450, 500 and 550 .deg. C) and feed particle size (90generation. In the combined process (slow pyrolysis of biomass followed by steam gasification of char), first slow pyrolysis is carried out at the effective conditions (pyrolysis temperature and particle size) of char generation (determined from bench scale study) and steam gasification is at varying gasification temperature (600, 650, 700, 750 and 800 .deg. C) and steam to biomass (S/B) ratio (1, 2, 3, 4, 5 and 6) to determine the effective conditions of H{sub 2} generation. The effect of temperature and S/B on gas product composition and overall product gas volume was also investigated. At effective conditions (gasification temperature and S/B) of H2 generation, individual slow pyrolysis and steam gasification were also experimented to evaluate the performance of combined process. The effective condition of H{sub 2} generation in combined process was found to be 800 .deg. C (gasification temperature) and 5 (S/B), respectively. The combined process produced 35.90% and 23.60% more gas volume (overall) than slow pyrolysis and steam gasification process, respectively. With respect to H{sub 2} composition, the combined process generated 72.37% more than slow pyrolysis and 17.91% more than steam gasification process.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Graphene-based materials: fabrication, characterization and application for the decontamination of wastewater and wastegas and hydrogen storage/generation.

    Science.gov (United States)

    Wang, Hou; Yuan, Xingzhong; Wu, Yan; Huang, Huajun; Peng, Xin; Zeng, Guangming; Zhong, Hua; Liang, Jie; Ren, Miaomiao

    2013-07-01

    Graphene, as an ideal two-dimensional material and single-atom layer of graphite, has attracted exploding interests in multidisciplinary research because of its unique structure and exceptional physicochemical properties. Especially, graphene-based materials offer a wide range of potentialities for environmental remediation and energy applications. This review shows an extensive overview of the main principles and the recent synthetic technologies about designing and fabricating various innovative graphene-based materials. Furthermore, an extensive list of graphene-based sorbents and catalysts from vast literature has been compiled. The adsorptive and catalytic properties of graphene-based materials for the removal of various pollutants and hydrogen storage/production as available in the literature are presented. Tremendous adsorption capacity, excellent catalytic performance and abundant availability are the significant factors making these materials suitable alternatives for environmental pollutant control and energy-related system, especially in terms of the removal of pollutants in water, gas cleanup and purification, and hydrogen generation and storage. Meanwhile, a brief discussion is also included on the influence of graphene materials on the environment, and its toxicological effects. Lastly, some unsolved subjects together with major challenges in this germinating area of research are highlighted and discussed. Conclusively, the expanding of graphene-based materials in the field of adsorption and catalysis science represents a viable and powerful tool, resulting in the superior improvement of environmental pollution control and energy development.

  12. Estimate Of The Decay Rate Constant of Hydrogen Sulfide Generation From Landfilled Drywall

    Science.gov (United States)

    Research was conducted to investigate the impact of particle size on H2S gas emissions and estimate a decay rate constant for H2S gas generation from the anaerobic decomposition of drywall. Three different particle sizes of regular drywall and one particle size of paperless drywa...

  13. Concurrent desalination and hydrogen generation using microbial electrolysis and desalination cells.

    Science.gov (United States)

    Luo, Haiping; Jenkins, Peter E; Ren, Zhiyong

    2011-01-01

    The versatility of bioelectrochemical systems (BESs) makes them promising for various applications, and good combinations could make the system more applicable and economically effective. An integrated BES called microbial electrolysis and desalination cell (MEDC) was developed to concurrently desalinate salt water, produce hydrogen gas, and potentially treat wastewater. The reactor is divided into three chambers by inserting a pair of ion exchange membranes, with each chamber serving one of the three functions. With an added voltage of 0.8 V, lab scale batch study shows the MEDC achieved the highest H(2) production rate of 1.5 m(3)/m(3) d (1.6 mL/h) from the cathode chamber, while also removing 98.8% of the 10 g/L NaCl from the middle chamber. The anode recirculation alleviated pH and high salinity inhibition on bacterial activity and further increased system current density from 87.2 to 140 A/m(3), leading to an improved desalination rate by 80% and H(2) production by 30%. Compared to slight changes in desalination, H(2) production was more significantly affected by the applied voltage and cathode buffer capacity, suggesting cathode reactions were likely affected by the external power supply in addition to the anode microbial activity.

  14. Ultrastable nitrogen-doped carbon encapsulating molybdenum phosphide nanoparticles as highly efficient electrocatalyst for hydrogen generation.

    Science.gov (United States)

    Pu, Zonghua; Amiinu, Ibrahim Saana; Liu, Xiaobo; Wang, Min; Mu, Shichun

    2016-10-06

    There is a crucial demand for cost-effective hydrogen evolution reaction (HER) catalysts towards future renewable energy systems, and the development of such catalysts operating under all pH conditions still remains a challenging task. In this work, a one-step facile approach to synthesizing nitrogen-doped carbon encapsulating molybdenum phosphide nanoparticles (MoP NPs@NC) is introduced by using ammonium molybdate, ammonium dihydrogen phosphate and melamine as precursor. Benefitting from structural advantages, including ultrasmall nanoparticles, large exposed surface area and fast charge transfer, MoP NPs@NC exhibits excellent HER catalytic activities with small overpotentials at all pH values (j = 10 mA cm(-2) at η = 115, 136 and 80 mV in 0.5 M H2SO4, 1.0 M phosphate buffer solution and 1.0 M KOH, respectively.). Meanwhile, the high catalytic activities of MoP NPs@NC under both neutral and basic conditions have never been achieved before for molybdenum phosphide-based catalysts. Additionally, the encapsulation by N-doped carbon effectively prevents the MoP NPs from corrosion, exhibiting nearly unfading stability after 100 h testing in 0.5 M H2SO4. Thus, our work could pave a new avenue for unprecedented design and fabrication of novel low-cost metal phosphide electrocatalysts encapsulated by N-doped carbon.

  15. 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.

  16. Understanding and Enhancing the Photostability of Nanoporous Metal Oxide Thin Films for Solar Hydrogen Generation

    Science.gov (United States)

    Chitrada, Kalyan Chakravarthi

    Solar water splitting is an environmentally benign process which has received wide attention in the recent years as an alternate method for a clean and safe production of hydrogen. This process employs a semiconductor based photocatalyst, water, and sunlight to produce hydrogen. Metal-oxide based semiconductors are considered to be ideal photocatalytic materials because of their stability against photo-corrosion combined with relatively narrow energy band-gap, appropriately placed band edge positions with reference to oxygen and hydrogen energy levels, less scattering of charges due to wider valence band, high dielectric constant, natural abundance, and non-toxicity. In this dissertation, two metal oxide based semiconductors viz., iron (III) oxide and bismuth (III) oxide were investigated to understand and enhance their photo activity as photoanodes for solar water splitting application. Iron (III) oxide has a well suited band gap to capture solar spectrum but it suffers from inappropriately positioned band edges, recombination losses due to low electron mobility, and a small minority carrier diffusion length. However, it was hypothesized that the Iron (III) oxide might show interesting photoelectrochemical properties by alloying with 4f elements and shifting the conduction band minimum of the iron oxide favorably to more negative potentials. In the present study, a nanoporous iron oxide layer incorporated with Nd3+ and B3+ was synthesized by electrochemical anodization of a FeNdB alloy. The photoelectrochemical behavior of this oxide was compared with thermally oxidized FeNdB alloy and the iron oxides obtained by anodization and thermal oxidation of pure iron foil. Incorporation of Nd3+ and B3+ in the iron oxide showed a direct bandgap of 2.05 eV, an indirect bandgap of 1.9 eV and shifted the flatband potentials to --0.8 VAg/AgCl in 1 M KOH solution. The FeNdB oxide showed marginally better catalytic activity for the oxygen evolution reaction than pure iron oxide

  17. 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.

  18. 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.

  19. Effect of nitrogen and intrinsic defect complexes on conversion efficiency of ZnO for hydrogen generation from water.

    Science.gov (United States)

    Lu, Y H; Russo, S P; Feng, Y P

    2011-09-21

    Band gap narrowing is important for applications of ZnO, especially for photoelectrochemical water splitting. In this work, we carried out first-principles electronic structure calculations with a hybrid density functional on defected ZnO. It is found that nitrogen substitutional doping alone cannot explain the largely enhanced conversion efficiency observed in nitrogen doped ZnO. Instead, complex defects formed by substitutional nitrogen and intrinsic defects play an important role in the band gap narrowing, in agreement with recent experimental results. We propose ZnO fabricated in a Zn-rich environment with heavy nitrogen doping as a photocatalyst for hydrogen generation from water splitting. A method for controlling the band gap of ZnO is also proposed.

  20. 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.

  1. 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.

  2. 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.

  3. Hydrogen peroxide generated by NADPH oxidase is involved in high blue-light-induced chloroplast avoidance movements in Arabidopsis

    Science.gov (United States)

    Wen, Feng; Xing, Da; Zhang, Lingrui

    2009-08-01

    One of the most important functions of blue light is to induce chloroplast movements by reducing the damage to photosynthetic machinery under excess light. Hydrogen peroxide (H2O2), generated by various environmental stimuli, can act as a signaling molecule that regulates a number of developmental processes and environmental responses. To investigate whether H2O2 is involved in high blue light-induced chloroplast avoidance movements, we use luminescence spectrometer to observe H2O2 generation with the assistance of the fluorescence probe dichlorofluorescin diacetate (H2DCF-DA). After treatment with high blue light, a large quantity of H2O2 indicated by the fluorescence intensity of DCF is produced in a dose-dependent manner in leaf strip of Arabidopsis. Enzymatic assay shows that the activity of NADPH oxidase, which is a major site for H2O2 generation, also rapidly increases in treated strips. Exogenously applied H2O2 can promote the high blue light-induced chloroplast movements. Moreover, high blue light-induced H2O2 generation can be abolished completely by addition of exogenous catalase (CAT), and partly by diphenylene iodonium (DPI) and dichlorophenyl dimethylurea (DCMU), which are an NADPH oxidase inhibitor and a blocker of electron transport chain. And subsequent chloroplast movements can be abolished by CAT and DPI, but not by DCMU. These results presented here suggested that high blue light can induce oxidative burst, and NADPH oxidase as a major producer for H2O2 is involved in blue light-induced chloroplast avoidance movements.

  4. Electrocemical Production of Ocean Alkalinity for Carbon Dioxide and Acid Mitigation, and Hydrogen Generation

    Science.gov (United States)

    Rau, G. H.

    2008-12-01

    Various schemes have been proposed to increase air-to-sea CO2 transfer and storage, including the addition of alkalinity to the ocean. Examples include the addition of: Ca(OH)2 derived from the thermal calcination of limestone (Kheshgi, 1995), NaOH from the electrochemical splitting of salt (House et al., 2007), and CaCO3 to carbonate-undersaturated waters (Harvey, 2008). Diluted in the ocean (to pH1/2O2+H2+Ca(HCO3)2aq. Laboratory experiments showed that such a system can generate excess alkalinity and elevated pH in seawater that subsequently allowed the absorption of 0.8 mM atmospheric CO2. Thus at larger scales, wind-, wave-, or solar-powered, fixed/floating platforms at the shoreline, in coastal waters, or in the open ocean might be employed to electrochemically increase ocean alkalinity. Such platforms would then: 1) enhance the ocean's natural absorption of atmospheric CO2, 2) help neutralize or offset the effects of ongoing ocean acidification, via the calcium hydroxide and/or bicarbonate production, and 3) generate carbon-negative H2 in the ratio 22kg CO2 absorbed/kg H2 produced.

  5. 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.

  6. 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.

  7. 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.

  8. 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)

  9. 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.

  10. 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.

  11. Method and apparatus for hydrogen production from water

    Science.gov (United States)

    Muradov, Nazim Z. (Inventor)

    2012-01-01

    A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

  12. 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)

  13. 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.

  14. 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%.

  15. 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.

  16. 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.

  17. Next Generation Hydrogen Station Composite Data Products: All Stations (Retail and Non-Retail Combined), Data through Quarter 3 of 2016

    Energy Technology Data Exchange (ETDEWEB)

    Sprik, Sam [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kurtz, Jennifer [National Renewable Energy Lab. (NREL), Golden, CO (United States); Ainscough, Chris [National Renewable Energy Lab. (NREL), Golden, CO (United States); Saur, Genevieve [National Renewable Energy Lab. (NREL), Golden, CO (United States); Peters, Michael [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jeffers, Matthew [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2017-03-06

    This publication includes 87 composite data products (CDPs) produced for next generation hydrogen stations with data through the third quarter of 2016. These CDPs include data for all stations in NREL's evaluation (retail and non-retail combined).

  18. 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.

  19. The relationship between the boron dipyrromethene (BODIPY) structure and the effectiveness of homogeneous and heterogeneous solar hydrogen-generating systems as well as DSSCs.

    Science.gov (United States)

    Luo, Geng-Geng; Lu, Hui; Zhang, Xiao-Long; Dai, Jing-Cao; Wu, Ji-Huai; Wu, Jia-Jia

    2015-04-21

    A series of boron dipyrromethene (BODIPY) dyes (B1–B5) having H atoms at 2,6-positions or heavy-atom I at 2-/2,6-positions, and an ortho- or a para-COOH substituted phenyl moiety at the 8-position on the BODIPY core were synthesized and characterized. These organic dyes were applied for investigating the relationship between the BODIPY structure and the effectiveness of homogeneous and heterogeneous visible-light-driven hydrogen production as well as dye-sensitized solar cells (DSSCs). For the homogeneous photocatalytic hydrogen production systems with a cobaloxime catalyst, the efficiency of hydrogen production could be tuned by substituting with heavy atoms and varying carboxyl group orientations of BODIPYs. As a result, B5 containing two I atoms and an ortho-COOH anchoring group was the most active one (TONs = 197). The activity of hydrogen generation followed the order B5 > B3 > B2 > B1 = B4 = 0. An interesting “ortho-position effect” was observed in the present homogeneous systems, i.e., substitution groups were located at the ortho-position and higher hydrogen production activities were obtained. For the heterogeneous hydrogen production systems with a platinized TiO2 catalyst, the effectiveness of hydrogen evolution was highly influenced by the intersystem crossing efficiency, molar absorptivity and positions of the anchoring group of dyes. Thus, B3 having two core iodine atoms and a para-COOH group with TONs of 70 excelled other BODIPYs and the TONs of hydrogen generation showed the trend of B3 > B5 > B2 > B1 = B4 = 0. The results demonstrate that the present photocatalytic H2 production proceeds with higher efficiency and stability in the homogeneity than in the heterogeneity. In the case of DSSCs, the overall cell performance of BODIPY chromophores was highly dependent on both the absence or the presence of iodine atoms on the BODIPY core and –COOH anchoring positions. The B1–TiO2 system showed the best cell performance, because the most

  20. Hydrogen peroxide generation in a model paediatric parenteral amino acid solution.

    Science.gov (United States)

    Brawley, V; Bhatia, J; Karp, W B

    1993-12-01

    1. Parenteral amino acid solutions undergo photooxidation, which may be an important factor in total parenteral nutrition-associated hepatic dysfunction. Light-exposed parenteral solutions containing amino acids, in addition to vitamins and trace minerals, generate free radicals, which, in turn, may contribute to this type of injury. This study examined the characteristics of H2O2 production in a parenteral amino acid solution modelled on a commercially available paediatric parenteral amino acid solution. 2. The solution was exposed to light in the presence of riboflavin-5'-monophosphate (riboflavin), and peroxide formation in the presence and absence of catalase (H2O2 formation) was assayed using potassium iodide/molybdate. 3. Peak H2O2 production occurred at a light intensity of 8 microW cm-2 nm-1 in the 425-475 nm waveband and was linear to 2 h of light exposure. H2O2 production reached 500 mumol/l at 24 h. 4. H2O2 was directly related to a riboflavin concentration of up to 20 mumol/l and was maximal at 30 mumol/l. 5. H2O2 production was greatest in the amino acid/riboflavin solution at a pH of between 5 and 6. 6. Under the conditions of light exposure intensity, light exposure time, riboflavin concentration and pH found during the administration of parenteral nutrition in neonatal intensive care units, net H2O2 production occurs in solutions modelled on a paediatric parenteral amino acid preparation.

  1. Hydrogen generation by metal corrosion in simulated Waste Isolation Pilot Plant environments. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Telander, M.R.; Westerman, R.E. [Battelle Pacific Northwest Lab., Richland, WA (United States)

    1997-03-01

    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 N{sub 2}, CO{sub 2}, H{sub 2}S, and H{sub 2}. 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 H{sub 2} on an equimolar basis with Fe reacted. Presence of CO{sub 2} caused the initial reaction to proceed more rapidly, but CO{sub 2}-induced passivation stopped the reaction if the CO{sub 2} were present in sufficient quantities. Addition of H{sub 2}S to a CO{sub 2}-passivated system caused reversal of the passivation. Low-carbon steel immersed in brine with H{sub 2}S showed no reaction, apparently because of passivation of the steel by formation of FeS. Addition of CO{sub 2} to an H{sub 2}S-passivated system did not reverse the passivation. Cu- and Ti-base materials showed essentially no corrosion when exposed to brine and overpressures of N{sub 2}, CO{sub 2}, and H{sub 2}S except for the rapid and complete reaction between Cu-base materials and H{sub 2}S. 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 CO{sub 2} or H{sub 2}S; 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.

  2. 水溶性金属卟啉催化过氧化氢氧化对苯二酚的动力学研究%Kinetics Studies on Oxidation of Hydroquinone Catalyzed by Water-soluble Metalloporphrin with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    卢燕; 谢斌; 黄春; 何锡阳; 邹立科; 林肖; 王艳美

    2011-01-01

    The kinetics of oxidative reaction of hydroquinone (HQ) with hydrogen peroxide catalyzed by water-soluble metalloporphyrins, Fe (TPPS) Cl and Co (TPPS) where TPPS = tetra (p-sulfonate) porphyrin, were studied by means of UV-vis spectrophotometer at 25℃. The acidity of the system, hydrogen peroxide / catalyst molar ratio and metal ions on the catalytic reaction were investigated. The oxidative mechanism of hydroquinone catalyzed by metalloporphyrin was proposed, and a kinetic model was established. The results show that Fe (TPPS)C1 and Co (TPPS) exhibit peroxidase-catalyzed oxidation characteristics. Therefore, the use of metalloporphyrin as peroxidase in the simulation process of hydroquinone oxidation is an effective catalyst.%我们利用紫外-可见分光光度法研究了25℃时金属卟啉Fe(TPPS)Cl和Co(TPPS)催化过氧化氢氧化对苯二酚(HQ)的动力学(其中,TPPS为四(p-磺酸钠苯基)卟啉),探讨了体系酸度、过氧化氢/催化剂摩尔比、中心金属离子对催化反应的影响,提出了金属卟啉催化氧化对苯二酚的反应历程,建立了反应的动力学模型.研究结果表明:Fe(TPPS)Cl和Co(TPPS)表现出过氧化物酶的催化氧化特性.因此,所用金属卟啉作为模拟过氧化物酶催化氧化HQ是一种有效的催化剂.

  3. Iridium-Catalyzed Allylic Substitution

    Science.gov (United States)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

  4. 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.

  5. Hydrogenation of the alpha,beta-unsaturated aldehydes acrolein, crotonaldehyde, and prenal over Pt single crystals: a kinetic and sum-frequency generation vibrational spectroscopy study.

    Science.gov (United States)

    Kliewer, Christopher J; Bieri, Marco; Somorjai, Gabor A

    2009-07-29

    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 of aldehyde, 100 Torr of hydrogen) in the temperature range of 295-415 K. SFG-VS data showed that acrolein has mixed adsorption species of eta(2)-di-sigma(CC)-trans, eta(2)-di-sigma(CC)-cis as well as highly coordinated eta(3) or eta(4) species. Crotonaldehyde adsorbed to Pt(111) as eta(2) surface intermediates. SFG-VS during prenal hydrogenation also suggested the presence of the eta(2) adsorption species and became more highly coordinated as the temperature was raised to 415 K, 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, crotyl alcohol.

  6. Silver nanoparticles sensitized C60(Ag@C60) as efficient electrocatalysts for hydrazine oxidation: Implication for hydrogen generation reaction

    Science.gov (United States)

    Narwade, Shankar S.; Mulik, Balaji B.; Mali, Shivsharan M.; Sathe, Bhaskar R.

    2017-02-01

    Herein, we report the synthesis of silver nanoparticles (Ag NPs; 10 ± 0.5 nm) sensitized Fullerene (C60; 15 ±2 nm) nanocatalysts (Ag@C60) for the first time showing efficient electroatalytic activity for the oxidation of hydrazine demonstrating activity comparable to that of Pt in acidic, neutral and basic media. The performance is comparable with the best available electrocatalytic system and plays a vital role in the overall hydrogen generation reactions from hydrazine as a one of the fuel cell reaction. The materials are synthesized by a simple and scalable synthetic route involving acid functionalization of C60 followed by chemical reduction of Ag+ ions in ethylene glycol at high temperature. The distributation of Silver nanoparticles (Ag NPs) (morphological information) on C60, bonding, its crystal structure, along with activity towards hydrazine oxidation (electrocatalytic) is studied using TEM, XRD, UV-vis, XPS, FTIR and electrochemical (cyclic voltammetry) studies, respectively. The observed efficient electrocatalytic activity of the as-synthesized electrode is attributed to the co-operative response and associated structural defects due to their oxidative functionalization along with thier cooperative functioning at nanodimensions.

  7. 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.

  8. 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.

  9. Numerical study of a jet-in-hot-coflow burner with hydrogen-addition using the Flamelet Generated Manifolds technique

    Science.gov (United States)

    Abtahizadeh, Seyed Ebrahim; van Oijen, Jeroen; de Goey, Philip

    2012-11-01

    Recently Mild combustion is subjected to intensive research because of its unique ability to provide high efficiency and low pollutant combustion simultaneously in industrial heating processes. In most practical Mild combustion applications, a fuel jet is ignited due to recirculation of hot burned gases. The impact of burned gases on autoignition and flame stabilization has been studied in a laboratory jet-in-hot-coflow (JHC) burner. Results of this study help us to understand recent experimental observations of the Delft group (DJHC burner) in which Dutch Natural Gas (DNG) is mixed with various amounts of H2. The main focus is on the modeling of autoignition in the DJHC burner by using the Flamelet Generated Manifolds (FGM) technique. In this technique, kinetic information is tabulated with a few controlling variables which results in a significant decrease in simulation time. The FGM tabulation has been performed using igniting laminar counterflow diffusion flames. Since H2 is present in the fuel composition, it is essential to include preferential diffusion effects in the table due to the high diffusivity of H2. Based on results, the FGM table is capable to reproduce the autoignition of hydrogen containing fuel predicted by detailed chemistry in 1D counterflow flames. The Authors gratefully acknowledge financial support of the Dutch Technology Foundation STW.

  10. 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.

  11. 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.

  12. Hydrogen carriers

    Science.gov (United States)

    He, Teng; Pachfule, Pradip; Wu, Hui; Xu, Qiang; Chen, Ping

    2016-12-01

    Hydrogen has the potential to be a major energy vector in a renewable and sustainable future energy mix. The efficient production, storage and delivery of hydrogen are key technical issues that require improvement before its potential can be realized. In this Review, we focus on recent advances in materials development for on-board hydrogen storage. We highlight the strategic design and optimization of hydrides of light-weight elements (for example, boron, nitrogen and carbon) and physisorbents (for example, metal-organic and covalent organic frameworks). Furthermore, hydrogen carriers (for example, NH3, CH3OH-H2O and cycloalkanes) for large-scale distribution and for on-site hydrogen generation are discussed with an emphasis on dehydrogenation catalysts.

  13. 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.

  14. CALCULATION OF CONDITIONAL EQUILIBRIUM IN SERIAL MULTIPLE PRECIPITATION OF METAL SULFIDES WITH HYDROGEN SULFIDE STREAM GENERATED FROM SODIUM SULFIDE: A DIDACTIC TOOL FOR CHEMISTRY TEACHING

    Directory of Open Access Journals (Sweden)

    Renata Bellová

    2016-07-01

    Full Text Available Hydrogen sulfide is presented in textbooks as toxic, environmentally unacceptable species, however some positive effects in human metabolism were discovered in the last decades. It is important to offer students also some new information about this compound. As didactic tool in this case may serve serial precipitation of Cd2+, Cu2+, Zn2+, Mn2+ and Pb2+ ions forming various colored sulfides in bubblers with chemically generated hydrogen sulfide stream. This experiment has strong and diverse color effect for enhancing the visual perception to motivate students to understand more abstract and complex information about hydrogen sulfide. It also may be helpful in analytical chemistry courses for conditional precipitation equilibrium teaching and calculations.

  15. 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.

  16. Electrochemical generation of hydrogen

    OpenAIRE

    Syed Khurram, Raza

    2017-01-01

    This thesis was submitted for the award of Doctor of Philosophy and was awarded by Brunel University London Global warming and the energy crisis are two of the greatest challenges on which mankind is currently focused. This has forced governments and other organisations to think how to protect the environment and how to reduce fuel costs. A variety of new and exciting technologies are being investigated to address the energy problem. Alternative energy sources such as solar power, fuel cel...

  17. 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

  18. Ruthenium-Catalyzed Ammonia Borane Dehydrogenation: Mechanism and Utility.

    Science.gov (United States)

    Zhang, Xingyue; Kam, Lisa; Trerise, Ryan; Williams, Travis J

    2017-01-17

    One of the greatest challenges in using H2 as a fuel source is finding a safe, efficient, and inexpensive method for its storage. Ammonia borane (AB) is a solid hydrogen storage material that has garnered attention for its high hydrogen weight density (19.6 wt %) and ease of handling and transport. Hydrogen release from ammonia borane is mediated by either hydrolysis, thus giving borate products that are difficult to rereduce, or direct dehydrogenation. Catalytic AB dehydrogenation has thus been a popular topic in recent years, motivated both by applications in hydrogen storage and main group synthetic chemistry. This Account is a complete description of work from our laboratory in ruthenium-catalyzed ammonia borane dehydrogenation over the last 6 years, beginning with the Shvo catalyst and resulting ultimately in the development of optimized, leading catalysts for efficient hydrogen release. We have studied AB dehydrogenation with Shvo's catalyst extensively and generated a detailed understanding of the role that borazine, a dehydrogenation product, plays in the reaction: it is a poison for both Shvo's catalyst and PEM fuel cells. Through independent syntheses of Shvo derivatives, we found a protective mechanism wherein catalyst deactivation by borazine is prevented by coordination of a ligand that might otherwise be a catalytic poison. These studies showed how a bidentate N-N ligand can transform the Shvo into a more reactive species for AB dehydrogenation that minimizes accumulation of borazine. Simultaneously, we designed novel ruthenium catalysts that contain a Lewis acidic boron to replace the Shvo -OH proton, thus offering more flexibility to optimize hydrogen release and take on more general problems in hydride abstraction. Our scorpionate-ligated ruthenium species (12) is a best-of-class catalyst for homogeneous dehydrogenation of ammonia borane in terms of its extent of hydrogen release (4.6 wt %), air tolerance, and reusability. Moreover, a synthetically

  19. Multifunctional silicon surfaces: reaction of dichlorocarbene generated from Seyferth reagent with hydrogen-terminated silicon (111) surfaces.

    Science.gov (United States)

    Liu, Wenjun; Sharp, Ian D; Tilley, T Don

    2014-01-14

    Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si-H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering ∼25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2Br provides a facile route to multifunctional surfaces possessing both stable silicon-carbon and labile silicon-halogen sites, in a single pot synthesis. The reactive silicon-halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic-silicon hybrid systems.

  20. 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

  1. 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.

  2. 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...

  3. 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.

  4. 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.

  5. Cu2ZnSnS4/MoS2-Reduced Graphene Oxide Heterostructure: Nanoscale Interfacial Contact and Enhanced Photocatalytic Hydrogen Generation

    Science.gov (United States)

    Ha, Enna; Liu, Wei; Wang, Luyang; Man, Ho-Wing; Hu, Liangsheng; Tsang, Shik Chi Edman; Chan, Chris Tsz-Leung; Kwok, Wai-Ming; Lee, Lawrence Yoon Suk; Wong, Kwok-Yin

    2017-01-01

    Hydrogen generation from water using noble metal-free photocatalysts presents a promising platform for renewable and sustainable energy. Copper-based chalcogenides of earth-abundant elements, especially Cu2ZnSnS4 (CZTS), have recently arisen as a low-cost and environment-friendly material for photovoltaics and photocatalysis. Herein, we report a new heterostructure consisting of CZTS nanoparticles anchored onto a MoS2-reduced graphene oxide (rGO) hybrid. Using a facile two-step method, CZTS nanoparticles were in situ grown on the surface of MoS2-rGO hybrid, which generated high density of nanoscale interfacial contact between CZTS and MoS2-rGO hybrid. The photoexcited electrons of CZTS can be readily transported to MoS2 through rGO backbone, reducing the electron-hole pair recombination. In photocatalytic hydrogen generation under visible light irradiation, the presence of MoS2-rGO hybrids enhanced the hydrogen production rate of CZTS by 320%, which can be attributed to the synergetic effect of increased charge separation by rGO and more catalytically active sites from MoS2. Furthermore, this CZTS/MoS2-rGO heterostructure showed much higher photocatalytic activity than both Au and Pt nanoparticle-decorated CZTS (Au/CZTS and Pt/CZTS) photocatalysts, indicating the MoS2-rGO hybrid is a better co-catalyst for photocatalytic hydrogen generation than the precious metal. The CZTS/MoS2-rGO system also demonstrated stable photocatalytic activity for a continuous 20 h reaction.

  6. ROLE OF COPPER,ZINC-SUPEROXIDE DISMUTASE IN CATALYZING NITROTYROSINE FORMATION IN MURINE LIVER

    Science.gov (United States)

    The solely known function of Cu,Zn-superoxide dismutase (SOD1) is to catalyze the dismutation of superoxide anion into hydrogen peroxide. Our objective was to determine if SOD1 catalyzed murine liver protein nitration induced by acetaminophen (APAP) and lipopolysaccharide (LPS). Liver and plasma ...

  7. Highly enantioselective [4 + 2] cyclization of chloroaldehydes and 1-azadienes catalyzed by N-heterocyclic carbenes.

    Science.gov (United States)

    Jian, Teng-Yue; Sun, Li-Hui; Ye, Song

    2012-11-14

    Highly functionalized dihydropyridinones were synthesized via the N-heterocyclic carbene-catalyzed enantioselective [4 + 2] annulation of α-chloroaldehydes and azadienes. Hydrogenation of the resulted dihydropyridinones afforded the corresponding piperidinones with high enantiopurity.

  8. 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 [Iowa State Univ., Ames, IA (United States)

    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.

  9. 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.

  10. Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

    Science.gov (United States)

    Huang, C. J.; Yeager, E.; Ogrady, W. E.

    1975-01-01

    The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  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. 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.)

  19. 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.

  20. A rechargeable hydrogen battery based on Ru catalysis.

    Science.gov (United States)

    Hsu, Shih-Fan; Rommel, Susanne; Eversfield, Philipp; Muller, Keven; Klemm, Elias; Thiel, Werner R; Plietker, Bernd

    2014-07-01

    Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H2 battery which is based on the principle of the Ru-catalyzed hydrogenation of CO2 to formic acid (charging process) and the Ru-catalyzed decomposition of formic acid to CO2 and H2 (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure-free conditions (discharging process). Up to five charging-discharging cycles were performed without decrease of storage capacity. The resulting CO2/H2 mixture is free of CO and can be employed directly in fuel-cell technology.