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Sample records for metal catalyzed hydrogen

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

    International Nuclear Information System (INIS)

    King, R.B.; Bhattacharyya, N.K.; Wiemers, K.D.

    1994-08-01

    Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 -, and NO 2 - were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO 2 H → H 2 + CO 2 catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100 degree C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl 3 ·3H 2 O, was found to be the most active catalyst for hydrogen generation from formic acid above ∼80 degree C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature (∼90 degree C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO 2 and NO/N 2 O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion

  2. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang

    2018-04-04

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  3. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

    2018-01-01

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  4. AB/sub 5/-catalyzed hydrogen evolution cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Hall, D E; Sawada, T; Shepard, V R; Tsujikawa, Y

    1984-01-01

    The AB/sub 5/ metal compounds are highly efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Three types of AB/sub 5/-catalyzed cathode structures were made, using the hydride-forming AB/sub 5/ compounds in particulate form. Plastic-bonded cathodes containing >90 w/o AB/sub 5/ (finished-weight basis) were the most efficient, giving hydrogen evolution overpotentials (/eta/ /SUB H2/ ) of about 0.05 V at 200 mA cm/sup -2/. However, they tended to swell and shed material during electrolysis. Pressed, sintered cathodes containing 40-70 w/o catalyst in a nickel binder gave /eta/ /SUB H2/ about0.08 V; catalyst retention was excellent. Porous, sintered cathode coatings were made with 30-70 w/o AB/sub 5/ catalyst loadings. Their overpotentials were similar to those of the pressed, sintered cathodes. However, at catalyst loadings below about 40 w/o, high overpotentials characteristic of the nickel binder were observed. The structural and electrochemical properties of the three AB/sub 5/-catalyzed cathodes are discussed.

  5. Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium-Catalyzed Asymmetric Hydrogenation.

    Science.gov (United States)

    Guan, Yanfei; Wheeler, Steven E

    2017-07-24

    A computational toolkit (AARON: An automated reaction optimizer for new catalysts) is described that automates the density functional theory (DFT) based screening of chiral ligands for transition-metal-catalyzed reactions with well-defined reaction mechanisms but multiple stereocontrolling transition states. This is demonstrated for the Rh-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, for which a new C 2 -symmetric phosphorus ligand is designed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    Science.gov (United States)

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. New Transition metal assisted complex borohydrides for hydrogen storage

    International Nuclear Information System (INIS)

    Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

    2006-01-01

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH 4 ) 2 ] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

  9. Complementary Strategies for Directed C(sp3 )-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer.

    Science.gov (United States)

    Chu, John C K; Rovis, Tomislav

    2018-01-02

    The functionalization of C(sp 3 )-H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C-H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition-metal-catalyzed C-H activation, 1,n-hydrogen atom transfer, and transition-metal-catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp 3 )-H bonds. For each strategy, the scope, the reactivity of different C-H bonds, the position of the reacting C-H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C-H functionalization reactions and inspire future research in this area. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Honggang Chang

    2015-10-01

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

  11. Applications of ion implantation for modifying the interactions between metals and hydrogen gas

    Science.gov (United States)

    Musket, R. G.

    1989-04-01

    Ion implantations into metals have been shown recently to either reduce or enhance interactions with gaseous hydrogen. Published studies concerned with modifications of these interactions are reviewed and discussed in terms of the mechanisms postulated to explain the observed changes. The interactions are hydrogenation, hydrogen permeation, and hydrogen embrittlement. In particular, the results of the reviewed studies are (a) uranium hydriding suppressed by implantation of oxygen and carbon, (b) hydrogen gettered in iron and nickel using implantation of titanium, (c) hydriding of titanium catalyzed by implanted palladium, (d) tritium permeation of 304L stainless steel reduced using selective oxidation of implanted aluminum, and (e) hydrogen attack of a low-alloy steel accelerated by implantation of helium. These studies revealed ion implantation to be an effective method for modifying the interactions of hydrogen gas with metals.

  12. Applications of ion implantation for modifying the interactions between metals and hydrogen gas

    International Nuclear Information System (INIS)

    Musket, R.G.

    1989-01-01

    Ion implantations into metals have been shown recently to either reduce or enhance interactions with gaseous hydrogen. Published studies concerned with modifications of these interactions are reviewed and discussed in terms of the mechanisms postulated to explain the observed changes. The interactions are hydrogenation, hydrogen permeation and hydrogen embrittlement. In particular, the results of the reviewed studies are 1. uranium hydriding suppressed by implantation of oxygen and carbon, 2. hydrogen gettered in iron and nickel using implantation of titanium, 3. hydriding of titanium catalyzed by implanted palladium, 4. tritium permeation of 304L stainless steel reduced using selective oxidation of implanted aluminum, and 5. hydrogen attack of a low-alloy steel accelerated by implantation of helium. These studies revealed ion implantation to be an effective method for modifying the interactions of hydrogen gas with metals. (orig.)

  13. 1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

    International Nuclear Information System (INIS)

    Esaki, N.; Nakayama, T.; Sawada, S.; Tanaka, H.; Soda, K.

    1985-01-01

    Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically

  14. Catalyzed borohydrides for hydrogen storage

    Science.gov (United States)

    Au, Ming [Augusta, GA

    2012-02-28

    A hydrogen storage material and process is provided in which alkali borohydride materials are created which contain effective amounts of catalyst(s) which include transition metal oxides, halides, and chlorides of titanium, zirconium, tin, and combinations of the various catalysts. When the catalysts are added to an alkali borodydride such as a lithium borohydride, the initial hydrogen release point of the resulting mixture is substantially lowered. Additionally, the hydrogen storage material may be rehydrided with weight percent values of hydrogen at least about 9 percent.

  15. The conversion of dimethyl ether over Pt/H-ZSM5. A bifunctional catalyzed reaction

    NARCIS (Netherlands)

    Engelen, C.W.R.; Wolthuizen, J.P.; Hooff, van J.H.C.; Imelik, B.; Naccache, C.; Coudurier, G.

    1985-01-01

    At low temperatures dimethylether mixed with hydrogen reacts over a platinum loaded H-ZSM5 catalyst selectivity to methane. Two successive steps can be distinguished; first the acid-catalyzed formation of a trimethyloxoniumion, followed by a metal-catalyzed hydrogenation to methane. Experiments with

  16. Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Vetter, Tiffany A.; Colombo, D. Philip, Jr.

    2003-07-01

    CIBA Vision Corporation markets a contact lens cleaning system that consists of an AOSEPT disinfectant solution and an AOSEPT lens cup. The disinfectant is a buffered 3.0% m/v hydrogen peroxide solution and the cup includes a platinum-coated AOSEPT disc. The hydrogen peroxide disinfects by killing bacteria, fungi, and viruses found on the contact lenses. Because the concentration of hydrogen peroxide needed to disinfect is irritating to eyes, the hydrogen peroxide needs to be neutralized, or decomposed, before the contact lenses can be used again. A general chemistry experiment is described where the kinetics of the catalyzed decomposition of the hydrogen peroxide are studied by measuring the amount of oxygen generated as a function of time. The order of the reaction with respect to the hydrogen peroxide, the rate constant, and the energy of activation are determined. The integrated rate law is used to determine the time required to decompose the hydrogen peroxide to a concentration that is safe for eyes.

  17. Hydrogen-metal systems

    International Nuclear Information System (INIS)

    Wenzl, H.; Springer, T.

    1976-01-01

    A survey is given on the alloys of metal crystals with hydrogen. The system niobium-hydrogen and its properties are especially dealt with: diffusion and heat of solution of hydrogen in the host crystal, phase diagram, coherent and incoherent phase separation, application of metal-hydrogen systems in technology. Furthermore, examples from research work in IFF (Institut fuer Festkoerperforschung) of the Nuclear Research Plant, Juelich, in the field of metal-H systems are given in summary form. (GSC) [de

  18. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  19. TEM analysis of the microstructure in TiF3-catalyzed and pure MgH2 during the hydrogen storage cycling

    International Nuclear Information System (INIS)

    Danaie, Mohsen; Mitlin, David

    2012-01-01

    We utilized transmission electron microscopy (TEM) analysis, with a cryogenically cooled sample stage, to detail the microstructure of partially transformed pure and titanium fluoride-catalyzed magnesium hydride powder during hydrogenation cycling. The TiF 3 -catalyzed MgH 2 powder demonstrated excellent hydrogen storage kinetics at various temperatures, whereas the uncatalyzed MgH 2 showed significant degradation in both kinetics and capacity. TEM analysis on the partially hydrogen absorbed and partially desorbed pure Mg(MgH 2 ) revealed a large fraction of particles that were either not transformed at all or were completely transformed. On the other hand, in the MgH 2 +TiF 3 system it was much easier to identify regions with both the hydride and the metal phase coexisting in the same particle. This enabled us to establish the metal hydride orientation relationship (OR) during hydrogen absorption. The OR was determined to be (1 1 0)MgH 2 || (−1 1 0 −1)Mg and [−1 1 1]MgH 2 || [0 1 −1 1]Mg. During absorption the number density of the hydride nuclei does not show a dramatic increase due the presence of TiF 3 . Conversely, during desorption the TiF 3 catalyst substantially increases the number of the newly formed Mg crystallites, which display a strong texture correlation with respect to the parent MgH 2 phase. Titanium fluoride also promotes extensive twinning in the hydride phase.

  20. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    Science.gov (United States)

    Patki, Gauri Dilip

    mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

  1. Characteristics of hydrogen evolution and oxidation catalyzed by Desulfovibrio caledoniensis biofilm on pyrolytic graphite electrode

    International Nuclear Information System (INIS)

    Yu Lin; Duan Jizhou; Zhao Wei; Huang Yanliang; Hou Baorong

    2011-01-01

    Highlights: → The sulphate-reducing bacteria (SRB) have the ability to catalyze the hydrogen evolution and oxidation on pyrolytic graphite electrode. → The SRB biofilm decreases the overpotential and electron transfer resistance by the CV and EIS detection. → The SRB biofilm can transfer electrons to the 0.24 V polarized pyrolytic graphite electrode and the maximum current is 0.035 mA, which is attributed to SRB catalyzed hydrogen oxidation. → The SRB biofilm also can obtain electron from the -0.61 V polarized PGE to catalyze the hydrogen evolution. - Abstract: Hydrogenase, an important electroactive enzyme of sulphate-reducing bacteria (SRB), has been discovered having the capacity to connect its activity to solid electrodes by catalyzing hydrogen evolution and oxidation. However, little attention has been paid to similar electroactive characteristics of SRB. In this study, the electroactivities of pyrolytic graphite electrode (PGE) coated with SRB biofilm were investigated. Two corresponding redox peaks were observed by cyclic voltammetry detection, which were related to the hydrogen evolution and oxidation. Moreover, the overpotential for the reactions decreased by about 0.2 V in the presence of the SRB biofilm. When the PGE coated with the SRB biofilm was polarized at 0.24 V (vs. SHE), an oxidation current related to the hydrogen oxidation was found. The SRB biofilm was able to obtain electrons from the -0.61 V (vs. SHE) polarized PGE to form hydrogen, and the electron transfer resistance also decreased with the formation of SRB biofilm, as measured by the non-destructive electrochemical impendence spectroscopy detection. It was concluded that the hydrogen evolution and oxidation was an important way for the electron transfer between SRB biofilm and solid electrode in anaerobic environment.

  2. 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)

  3. New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

    Directory of Open Access Journals (Sweden)

    Georgiy B. Shul’pin

    2016-03-01

    Full Text Available This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst. Works of recent years (mainly 2010–2016 devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon–hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

  4. Oxidation of lignin-carbohydrate complex from bamboo with hydrogen peroxide catalyzed by Co(salen

    Directory of Open Access Journals (Sweden)

    Zhou Xue-Fei

    2014-01-01

    Full Text Available The reactivity of salen complexes toward hydrogen peroxide has been long recognized. Co(salen was tested as catalyst for the aqueous oxidation of a refractory lignin-carbohydrate complex (LCC isolated from sweet bamboo (Dendrocalamushamiltonii in the presence of hydrogen peroxide as oxidant. Co(salen catalyzed the reaction of hydrogen peroxide with LCC. From the spectra analyses, lignin units in LCC were undergoing ring-opening, side chain oxidation, demethoxylation, β-O-4 cleavage with Co(salen catalytic oxidation. The degradation was also observed in the carbohydrate of LCC. The investigation on the refractory LCC degradation catalyzed by Co(salen may be an important aspect for environmentally-oriented biomimetic bleaching in pulp and paper industry.

  5. Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

    Science.gov (United States)

    Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

    2014-08-04

    Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The behavior of hydrogen in metals

    International Nuclear Information System (INIS)

    Hirabayashi, Makoto

    1975-01-01

    Explanation is made on the equilibrium diagrams of metal-hydrogen systems and the state of hydrogen in metals. Some metals perform exothermic reaction with hydrogen, and the others endothermic reaction. The former form stable hydrides and solid solutions over a wide range of composition. Hydrogen atoms in fcc and bcc metals are present at the interstitial positions of tetrahedron lattice and octahedron lattice. For example, hydrogen atoms in palladium are present at the intersititial positions of octahedron. When the ratio of the composition of hydrogen and palladium is 1:1, the structure becomes NaCl type. Hydrogen atoms in niobium and vanadium and present interstitially in tetrahedron lattice. Metal hydrides with high hydrogen concentration are becoming important recently as the containers of hydrogen. Hydrogen atoms diffuse in metals quite easily. The activation energy of the diffusion of hydrogen atoms in Nb and V is about 2-3 kcal/g.atom. The diffusion coefficient is about 10 -5 cm 2 /sec in alpha phase at room temperature. The number of jumps of a hydrogen atom between neighboring lattice sites is 10 11 --10 12 times per second. This datum is almost the same as that of liquid metals. Discussion is also made on the electronic state of hydrogen in metals. (Fukutomi, T.)

  7. An optimized hydrogen target for muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Gheisari, R., E-mail: gheisari@pgu.ac.i [Physics Department, Persian Gulf University, Bushehr 75169 (Iran, Islamic Republic of)

    2011-04-01

    This paper deals with the optimization of the processes involved in muon catalyzed fusion. Muon catalyzed fusion ({mu}CF) is studied in all layers of the solid hydrogen structure H/0.1%T+D{sub 2}+HD. The layer H/T acts as an emitter source of energetic t{mu} atoms, due to the so-called Ramsauer-Townsend effect. These t{mu} atoms are slowed down in the second layer (degrader) and are forced to take place nuclear fusion in HD. The degrader affects time evolution of t{mu} atomic beam. This effect has not been considered until now in {mu}CF-multilayered targets. Due to muon cycling and this effect, considerable reactions occur in the degrader. In our calculations, it is shown that the fusion yield equals 180{+-}1.5. It is possible to separate events that overlap in time.

  8. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

    A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.

  9. Synthesis of heterocycles via transition-metal-catalyzed hydroarylation of alkynes.

    Science.gov (United States)

    Yamamoto, Yoshihiko

    2014-03-07

    Transition-metal (TM)-catalyzed hydroarylation reactions of alkynes have received much attention, because they enable the net insertion of alkyne C-C triple bonds into C-H bonds of aromatic precursors, resulting in regio- and stereo-selective formation of synthetically useful arylalkenes. Taking advantage of this feature, TM-catalyzed alkyne hydroarylations have been successfully used for the synthesis of heterocycles. TM-catalyzed alkyne hydroarylations can be classified into three major categories depending on the type of reaction and precursors involved: (1) palladium-catalyzed reductive Heck reactions of alkynes with aryl halides, (2) TM-catalyzed conjugate arylation reactions of activated alkynes with arylboronic acids, and (3) TM-catalyzed aromatic C-H alkenylations with alkynes. This review surveys heterocycle synthesis via TM-catalyzed hydroarylation of alkynes according to the above classification, with an emphasis on the scope and limitations, as well as the underlying mechanisms.

  10. Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

    Science.gov (United States)

    Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

    2009-01-01

    One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

  11. Metallic hydrogen research

    International Nuclear Information System (INIS)

    Burgess, T.J.; Hawke, R.S.

    1978-01-01

    Theoretical studies predict that molecular hydrogen can be converted to the metallic phase at very high density and pressure. These conditions were achieved by subjecting liquid hydrogen to isentropic compression in a magnetic-flux compression device. Hydrogen became electrically conducting at a density of about 1.06 g/cm 3 and a calculated pressure of about 2 Mbar. In the experimental device, a cylindrical liner, on implosion by high explosive, compresses a magnetic flux which in turn isentropically compresses a hydrogen sample; coaxial conical anvils prevent escape of the sample during compression. One anvil contains a coaxial cable that uses alumina ceramic as an insulator; this probe allows continuous measurement of the electrical conductivity of the hydrogen. A flash x-ray radiograph exposed during the experiment records the location of the sample-tube boundaries and permits calculation of the sample density. The theoretical underpinnings of the metallic transition of hydrogen are briefly summarized, and the experimental apparatus and technique, analytical methods, and results are described. 9 figures

  12. Destabilized and catalyzed borohydride for reversible hydrogen storage

    Science.gov (United States)

    Mohtadi, Rana F [Northville, MI; Nakamura, Kenji [Toyota, JP; Au, Ming [Martinez, GA; Zidan, Ragaiy [Alken, SC

    2012-01-31

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

  13. Modeling evolution of hydrogen bonding and stabilization of transition states in the process of cocaine hydrolysis catalyzed by human butyrylcholinesterase.

    Science.gov (United States)

    Gao, Daquan; Zhan, Chang-Guo

    2006-01-01

    Molecular dynamics (MD) simulations and quantum mechanical/molecular mechanical (QM/MM) calculations were performed on the prereactive enzyme-substrate complex, transition states, intermediates, and product involved in the process of human butyrylcholinesterase (BChE)-catalyzed hydrolysis of (-)-cocaine. The computational results consistently reveal a unique role of the oxyanion hole (consisting of G116, G117, and A199) in BChE-catalyzed hydrolysis of cocaine, compared to acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylcholine. During BChE-catalyzed hydrolysis of cocaine, only G117 has a hydrogen bond with the carbonyl oxygen (O31) of the cocaine benzoyl ester in the prereactive BChE-cocaine complex, and the NH groups of G117 and A199 are hydrogen-bonded with O31 of cocaine in all of the transition states and intermediates. Surprisingly, the NH hydrogen of G116 forms an unexpected hydrogen bond with the carboxyl group of E197 side chain and, therefore, is not available to form a hydrogen bond with O31 of cocaine in the acylation. The NH hydrogen of G116 is only partially available to form a weak hydrogen bond with O31 of cocaine in some structures involved in the deacylation. The change of the estimated hydrogen-bonding energy between the oxyanion hole and O31 of cocaine during the reaction process demonstrates how the protein environment can affect the energy barrier for each step of the BChE-catalyzed hydrolysis of cocaine. These insights concerning the effects of the oxyanion hole on the energy barriers provide valuable clues on how to rationally design BChE mutants with a higher catalytic activity for the hydrolysis of (-)-cocaine. 2005 Wiley-Liss, Inc.

  14. Hydrogen permeation through metallic foils

    International Nuclear Information System (INIS)

    Bernardi, M.I.B.; Rodrigues, J.A.

    1987-01-01

    The process of electrolytic permeation of hydrogen through metallic foils is studied. A double electrolytic cell, in glass, in which the two compartments of reaction are separated by a metallic foil to be studied, was built. As direct result, the hydrogen diffusion coefficient in the metal is obtained. The hydrogen diffusion coefficients in the palladium and, in austenitic stainless steels 304 and 304 L, used in the Angra-1 reactor, were obtained. Samples of stainless steels with and without welding, were used. (Author) [pt

  15. Metal-ion catalyzed polymerization in the eutectic phase in water-ice

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.

    2008-01-01

    The emergence of an RNA world requires among other processes the non-enzymatic, template-directed replication of genetic polymers such as RNA or related nucleic acids, possibly catalyzed by metal ions. The absence of uridilate derivative polymerization on adenine containing templates has been...... the main issue preventing an efficient template-directed RNA polymerization. We report here the investigation of template-directed RNA polymerization in the eutectic phase in water-ice. In particular, it was found that activated Uridilate monomers in the presence of metal-ion catalysts could efficiently......-pairing opportunities. These results suggest that a template-directed RNA polymerization catalyzed by metal-ions could be carried out under eutectic phase in water-ice conditions....

  16. Metal hydrides for hydrogen storage in nickel hydrogen batteries

    International Nuclear Information System (INIS)

    Bittner, H.F.; Badcock, C.C.; Quinzio, M.V.

    1984-01-01

    Metal hydride hydrogen storage in nickel hydrogen (Ni/H 2 ) batteries has been shown to increase battery energy density and improve battery heat management capabilities. However the properties of metal hydrides in a Ni/H 2 battery environment, which contains water vapor and oxygen in addition to the hydrogen, have not been well characterized. This work evaluates the use of hydrides in Ni/H 2 batteries by fundamental characterization of metal hydride properties in a Ni/H 2 cell environment. Hydrogen sorption properties of various hydrides have been measured in a Ni/H 2 cell environment. Results of detailed thermodynamic and kinetic studies of hydrogen sorption in LaNi 5 in a Ni/H 2 cell environment are presented. Long-term cycling studies indicate that degradation of the hydride can be minimized by cycling between certain pressure limits. A model describing the mechanism of hydride degradation is presented

  17. Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols.

    Science.gov (United States)

    Chakraborty, Subrata; Das, Uttam Kumar; Ben-David, Yehoshoa; Milstein, David

    2017-08-30

    Catalytic α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles, is presented. The reaction is catalyzed by a pincer complex of an earth-abundant metal (manganese), in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.

  18. Chloride-catalyzed corrosion of plutonium in glovebox atmospheres

    International Nuclear Information System (INIS)

    Burgess, M.; Haschke, J.M.; Allen, T.H.; Morales, L.A.; Jarboe, D.M.; Puglisi, C.V.

    1998-04-01

    Characterization of glovebox atmospheres and the black reaction product formed on plutonium surfaces shows that the abnormally rapid corrosion of components in the fabrication line is consistent with a complex salt-catalyzed reaction involving gaseous hydrogen chloride (HCl) and water. Analytical data verify that chlorocarbon and HCl vapors are presented in stagnant glovebox atmospheres. Hydrogen chloride concentrations approach 7 ppm at some locations in the glovebox line. The black corrosion product is identified as plutonium monoxide monohydride (PuOH), a product formed by hydrolysis of plutonium in liquid water and salt solutions at room temperature. Plutonium trichloride (PuCl 3 ) produced by reaction of HCl at the metal surface is deliquescent and apparently forms a highly concentrated salt solution by absorbing moisture from the glovebox atmosphere. Rapid corrosion is attributed to the ensuing salt-catalyzed reaction between plutonium and water. Experimental results are discussed, possible involvement of hydrogen fluoride (HF) is examined, and methods of corrective action are presented in this report

  19. Asymmetric hydrogenation of quinolines catalyzed by iridium complexes of monodentate BINOL-derived phosphoramidites

    NARCIS (Netherlands)

    Mrsic, Natasa; Lefort, Laurent; Boogers, Jeroen A. F.; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.; Mršić, Nataša

    The monodentate BINOL-derived phosphoramidite PipPhos is used as ligand for the iridium-catalyzed asymmetric hydrogenation of 2- and 2,6-substituted quinolines. If tri-ortho-tolylphosphine and/or chloride salts are used as additives enantioselectivities are strongly enhanced up to 89%. NMR indicates

  20. Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

    Directory of Open Access Journals (Sweden)

    Grégory Landelle

    2013-11-01

    Full Text Available In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

  1. New efficient hydrogen process production from organosilane hydrogen carriers derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Brunel, Jean Michel [Unite URMITE, UMR 6236 CNRS, Faculte de Medecine et de Pharmacie, Universite de la Mediterranee, 27 boulevard Jean Moulin, 13385 Marseille 05 (France)

    2010-04-15

    While the source of hydrogen constitutes a significant scientific challenge, addressing issues of hydrogen storage, transport, and delivery is equally important. None of the current hydrogen storage options, liquefied or high pressure H{sub 2} gas, metal hydrides, etc.. satisfy criteria of size, costs, kinetics, and safety for use in transportation. In this context, we have discovered a methodology for the production of hydrogen on demand, in high yield, under kinetic control, from organosilane hydrogen carriers derivatives and methanol as co-reagent under mild conditions catalyzed by a cheap ammonium fluoride salt. Finally, the silicon by-products can be efficiently recycle leading to an environmentally friendly source of energy. (author)

  2. Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation

    Science.gov (United States)

    Patman, Ryan L.; Chaulagain, Mani Raj; Williams, Vanessa M.; Krische, Michael J.

    2011-01-01

    Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a–1i to furnish allylic alcohols 2a–2i, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a–6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m–2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a. PMID:19173651

  3. Silica metal-oxide vesicles catalyze comprehensive prebiotic chemistry.

    Science.gov (United States)

    Bizzarri, Bruno Mattia; Botta, Lorenzo; Pérez-Valverde, Maritza Iveth; Saladino, Raffaele; Di Mauro, Ernesto; Garcia Ruiz, Juan Manuel

    2018-03-30

    It has recently been demonstrated that mineral self-assembled structures catalyzing prebiotic chemical reactions may form in natural waters derived from serpentinization, a geological process widespread in the early stages of Earth-like planets. We have synthesized self-assembled membranes by mixing microdrops of metal solutions with alkaline silicate solutions in the presence of formamide (NH2CHO), a single carbon molecule, at 80ºC. We found that these bilayer membranes, made of amorphous silica and metal oxide-hydroxide nanocrystals, catalyze the condensation of formamide, yielding the four nucleobases of RNA, three aminoacids and several carboxylic acids in a single pot experiment. Besides manganese, iron and magnesium, two abundant elements in the earliest Earth crust that are key in serpentinization reactions, are enough to produce all these biochemical compounds. These results suggest that the transition from inorganic geochemistry to prebiotic organic chemistry is common on a universal scale and, most probably, earlier than ever thought for our planet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Fluorinated cobalt for catalyzing hydrogen generation from sodium borohydride

    Energy Technology Data Exchange (ETDEWEB)

    Akdim, O.; Demirci, U.B.; Brioude, A.; Miele, P. [Laboratoire des Multimateriaux et Interfaces, UMR 5615 CNRS Universite Lyon 1, Universite de Lyon, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France)

    2009-07-15

    The present paper reports preliminary results relating to a search for durable cobalt-based catalyst intended to catalyze the hydrolysis of sodium borohydride (NaBH{sub 4}). Fluorination of Co [Suda S, Sun YM, Liu BH, Zhou Y, Morimitsu S, Arai K, et al. Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts. Appl Phys A 2001; 72: 209-12.] has attracted our attention whereas the fluorination of Co boride has never been envisaged so far. Our first objective was to compare the reactivity of fluorinated Co with that of Co boride. We focused our attention on the formation of Co boride from fluorinated Co. Our second objective was to show the fluorination effect on the reactivity of Co. Our third objective was to find an efficient, durable Co catalyst. It was observed a limited stabilization of the Co surface by virtue of the fluorination, which made the formation of surface Co boride more difficult while the catalytic activity was unaltered. The fluorination did not affect the number of surface active sites. Nevertheless, it did not prevent the formation of Co boride. The fluorination of Co boride was inefficient. Hence, fluorination is a way to gain in stabilization of the catalytic surface but it is quite inefficient to hinder the boride formation. Accordingly, it did not permit to compare the reactivity of Co boride with that of Co. (author)

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

    NARCIS (Netherlands)

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

    2005-01-01

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

  6. 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

  7. The use of phosphite-type ligands in the Ir-catalyzed asymmetric hydrogenation of heterocyclic compounds.

    Science.gov (United States)

    Lyubimov, Sergey E; Ozolin, Dmitry V; Ivanov, Pavel Yu; Melman, Artem; Velezheva, Valeriya S; Davankov, Vadim A

    2014-01-01

    A series of chiral phosphite-type ligands was tested in asymmetric Ir-catalyzed hydrogenation of quinolines and 2,4,5,6-tetrahydro-1H-pyrazino(3,2,1-j,k)carbazole. Hydrogenation of quinaldine hydrochloride provided superior enantioselectivity up to 65% ee compared to quinaldine free base. The ligands were tested for the first time in the asymmetric Ir-Ircatalyzed hydrogenation of 2,4,5,6-tetrahydro-1H-pyrazino(3,2,1-j,k)carbazole yielding the antidepressant drug, pirlindole. © 2013 Wiley Periodicals, Inc.

  8. Hydrogenation of ethene catalyzed by Ir atom deposited on γ-Al2O3(001) surface: From ab initio calculations

    International Nuclear Information System (INIS)

    Chen, Yongchang; Sun, Zhaolin; Song, Lijuan; Li, Qiang; Xu, Ming

    2012-01-01

    Ethene hydrogenation reaction, catalyzed by an iridium atom adsorbed on γ-Al 2 O 3 (001) surface, is studied via ab initio calculations based on density functional theory (DFT). The catalyzed reaction process and activation energy are compared with the counterparts of a reaction occurs in vacuum condition. It is found that the activation energy barrier is substantially lowered by the adsorbed Ir atom on the γ-Al 2 O 3 (001). The catalyzed reaction is modeled in two steps: (1) Hydrogen molecular dissolution and then bonded with C 2 H 4 molecular. (2) Desorption of the C 2 H 6 molecular from the surface. -- Highlights: ► The ethene hydrogenation reaction is simulated with nudged elastic band methods. ► The catalytic effect of the Ir atom on γ-Al 2 O 3 (001) surface is modeled. ► Details of the catalytic reaction are exhibited.

  9. 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…

  10. High temperature equation of state of metallic hydrogen

    International Nuclear Information System (INIS)

    Shvets, V. T.

    2007-01-01

    The equation of state of liquid metallic hydrogen is solved numerically. Investigations are carried out at temperatures from 3000 to 20 000 K and densities from 0.2 to 3 mol/cm 3 , which correspond both to the experimental conditions under which metallic hydrogen is produced on earth and the conditions in the cores of giant planets of the solar system such as Jupiter and Saturn. It is assumed that hydrogen is in an atomic state and all its electrons are collectivized. Perturbation theory in the electron-proton interaction is applied to determine the thermodynamic potentials of metallic hydrogen. The electron subsystem is considered in the randomphase approximation with regard to the exchange interaction and the correlation of electrons in the local-field approximation. The proton-proton interaction is taken into account in the hard-spheres approximation. The thermodynamic characteristics of metallic hydrogen are calculated with regard to the zero-, second-, and third-order perturbation theory terms. The third-order term proves to be rather essential at moderately high temperatures and densities, although it is much smaller than the second-order term. The thermodynamic potentials of metallic hydrogen are monotonically increasing functions of density and temperature. The values of pressure for the temperatures and pressures that are characteristic of the conditions under which metallic hydrogen is produced on earth coincide with the corresponding values reported by the discoverers of metallic hydrogen to a high degree of accuracy. The temperature and density ranges are found in which there exists a liquid phase of metallic hydrogen

  11. Hydrogen peroxide safety issues

    International Nuclear Information System (INIS)

    Conner, W.V.

    1993-01-01

    A literature survey was conducted to review the safety issues involved in handling hydrogen peroxide solutions. Most of the information found in the literature is not directly applicable to conditions at the Rocky Flats Plant, but one report describes experimental work conducted previously at Rocky Flats to determine decomposition reaction-rate constants for hydrogen peroxide solutions. Data from this report were used to calculate decomposition half-life times for hydrogen peroxide in solutions containing several decomposition catalysts. The information developed from this survey indicates that hydrogen peroxide will undergo both homogeneous and heterogeneous decomposition. The rate of decomposition is affected by temperature and the presence of catalytic agents. Decomposition of hydrogen peroxide is catalyzed by alkalies, strong acids, platinum group and transition metals, and dissolved salts of transition metals. Depending upon conditions, the consequence of a hydrogen peroxide decomposition can range from slow evolution of oxygen gas to a vapor, phase detonation of hydrogen peroxide vapors

  12. 1-Butyl-3-methylimidazolium hydrogen sulfate catalyzed in-situ transesterification of Nannochloropsis to fatty acid methyl esters

    International Nuclear Information System (INIS)

    Sun, Yingqiang; Cooke, Peter; Reddy, Harvind K.; Muppaneni, Tapaswy; Wang, Jun; Zeng, Zheling; Deng, Shuguang

    2017-01-01

    Highlights: • [Bmim][HSO_4] catalyzed in-situ transesterification of wet algae. • [Bmim][HSO_4] served as both effective solvent and excellent acid catalyst. • Proposed a mechanism for [Bmim][HSO_4] catalyzed in-situ transesterification. • Identified cell walls and lipid droplets in algae using confocal imaging tests. • Obtained crude biodiesel yield about 95% in 30 min at 200 °C. - Abstract: 1-Butyl-3-methylimidazolium hydrogen sulfate ([Bmim][HSO_4]) is used as a solvent and an acid catalyst for in-situ extractive transesterification of wet Nannochloropsis with methanol. The reaction is supposed to be a five-step process: (1) wet algae cell wall dissolves in ionic liquid at reaction temperatures; (2) hydrogen ions and sulfate ions release from the ionization of HSO_4"−. The hydrogen ions (H"+) act as catalysts for accelerating the reactive extraction of triglyceride from wet Nannochloropsis; (3) hydrogen ions and methanol molecules transfer from bulk to active site of cells without passing through cell wall that is dissolved by ionic liquid; (4) in-situ transesterification of lipid (mainly triglycerides) with methanol; and (5) products transfer from inside of algae cells to outside of cells. The crude biodiesel yield of [Bmim][HSO_4] catalyzed in-situ transesterification is about 95.28% at reaction temperature of 200 °C, reaction time of 30 min, mass ratio of [Bmim][HSO_4] to wet Nannochloropsis of 0.9:1, and a mass ratio of methanol to wet algae of 3:1. It decreases to 81.23% after [Bmim][HSO_4] is recycled for 4 times, which indicates that [Bmim][HSO_4] catalyzed in-situ transesterification is an economic approach for biodiesel production from wet algae.

  13. Composite metal-hydrogen electrodes for metal-hydrogen batteries. Final report, October 1, 1993 - April 15, 1997

    International Nuclear Information System (INIS)

    Ruckman, M.W.; Strongin, M.; Weismann, H.

    1997-04-01

    The purpose of this project is to develop and conduct a feasibility study of metallic thin films (multilayered and alloy composition) produced by advanced sputtering techniques for use as anodes in Ni-metal hydrogen batteries that would be deposited as distinct anode, electrolyte and cathode layers in thin film devices. The materials could also be incorporated in secondary consumer batteries (i.e. type AF(4/3 or 4/5)) which use electrodes in the form of tapes. The project was based on pioneering studies of hydrogen uptake by ultra-thin Pd-capped Nb films, these studies suggested that materials with metal-hydrogen ratios exceeding those of commercially available metal hydride materials and fast hydrogen charging and discharging kinetics could be produced. The project initially concentrated on gas phase and electrochemical studies of Pd-capped niobium films in laboratory-scale NiMH cells. This extended the pioneering work to the wet electrochemical environment of NiMH batteries and exploited advanced synchrotron radiation techniques not available during the earlier work to conduct in-situ studies of such materials during hydrogen charging and discharging. Although batteries with fast charging kinetics and hydrogen-metal ratios approaching unity could be fabricated, it was found that oxidation, cracking and corrosion in aqueous solutions made pure Nb films and multilayers poor candidates for battery application. The project emphasis shifted to alloy films based on known elemental materials used for NiMH batteries. Although commercial NiMH anode materials contain many metals, it was found that 0.24 μm thick sputtered Zr-Ni films cycled at least 50 times with charging efficiencies exceeding 95% and [H]/[M] ratios of 0.7-1.0. Multilayered or thicker Zr-Ni films could be candidates for a thin film NiMH battery that may have practical applications as an integrated power source for modern electronic devices

  14. Solubility and diffusion of hydrogen in pure metals and alloys

    International Nuclear Information System (INIS)

    Wipf, H.

    2001-01-01

    Basic facts are presented of the absorption of hydrogen gas by metals and the diffusion of hydrogen in metals. Specifically considered are crystalline metals without defects and lattice disorder (pure metals), low hydrogen concentrations and the possibility of high hydrogen gas pressures. The first introductory topic is a short presentation of typical phase diagrams of metal hydrogen systems. Then, hydrogen absorption is discussed and shown to be decisively determined by the enthalpy of solution, in particular by its sign which specifies whether absorption is exothermic or endothermic. The formation of high-pressure hydrogen gas bubbles in a metal, which can lead to blistering, is addressed. It is demonstrated that bubble formation will, under realistic conditions, only occur in strongly endothermically hydrogen absorbing metals. The chief aspects of hydrogen diffusion in metals are discussed, especially the large size of the diffusion coefficient and its dependence on lattice structure. It is shown that forces can act on hydrogen in metals, causing a directed hydrogen flux. Such forces arise, for instance, in the presence of stress and temperature gradients and can result in local hydrogen accumulation with potential material failure effects. The final aspect discussed is hydrogen permeation, where the absorption behavior of the hydrogen is found to be in general more decisive on the permeation rate than the value of the diffusion coefficient. (orig.)

  15. Metal-functionalized silicene for efficient hydrogen storage.

    Science.gov (United States)

    Hussain, Tanveer; Chakraborty, Sudip; Ahuja, Rajeev

    2013-10-21

    First-principles calculations based on density functional theory are used to investigate the electronic structure along with the stability, bonding mechanism, band gap, and charge transfer of metal-functionalized silicene to envisage its hydrogen-storage capacity. Various metal atoms including Li, Na, K, Be, Mg, and Ca are doped into the most stable configuration of silicene. The corresponding binding energies and charge-transfer mechanisms are discussed from the perspective of hydrogen-storage compatibility. The Li and Na metal dopants are found to be ideally suitable, not only for strong metal-to-substrate binding and uniform distribution over the substrate, but also for the high-capacity storage of hydrogen. The stabilities of both Li- and Na-functionalized silicene are also confirmed through molecular dynamics simulations. It is found that both of the alkali metals, Li(+) and Na(+), can adsorb five hydrogen molecules, attaining reasonably high storage capacities of 7.75 and 6.9 wt %, respectively, with average adsorption energies within the range suitable for practical hydrogen-storage applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Enhanced hydrogen reaction kinetics of nanostructured Mg-based composites with nanoparticle metal catalysts dispersed on supports

    International Nuclear Information System (INIS)

    Yoo, Yeong; Tuck, Mark; Kondakindi, Rajender; Seo, Chan-Yeol; Dehouche, Zahir; Belkacemi, Khaled

    2007-01-01

    Hydrogen reaction kinetics of nanocrystalline MgH 2 co-catalyzed with Ba 3 (Ca 1+x Nb 2-x )O 9-δ (BCN) proton conductive ceramics and nanoparticle bimetallic catalyst of Ni/Pd dispersed on single wall carbon nanotubes (SWNTs) support has been investigated. The nanoparticle bimetallic catalysts of Ni/Pd supported by SWNTs were synthesized based on a novel polyol method using NiCl 2 .6H 2 O, PdCl 2 , NaOH and ethylene glycol (EG). The nanostructured Mg composites co-catalyzed with BCN and bimetallic supported catalysts exhibited stable hydrogen desorption capacity of 6.3-6.7 wt.% H 2 and the significant enhancement of hydrogen desorption kinetics at 230-300 deg. C in comparison to either non-catalyzed MgH 2 or the nanocomposite of MgH 2 catalyzed with BCN

  17. Towards hydrogen metallization: an Ab initio approach

    International Nuclear Information System (INIS)

    Bernard, St.

    1998-01-01

    The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H 2 ) 2 which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author)

  18. Final Report: Metal Perhydrides for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, J-Y.; Shi, S.; Hackney, S.; Swenson, D.; Hu, Y.

    2011-07-26

    Hydrogen is a promising energy source for the future economy due to its environmental friendliness. One of the important obstacles for the utilization of hydrogen as a fuel source for applications such as fuel cells is the storage of hydrogen. In the infrastructure of the expected hydrogen economy, hydrogen storage is one of the key enabling technologies. Although hydrogen possesses the highest gravimetric energy content (142 KJ/g) of all fuels, its volumetric energy density (8 MJ/L) is very low. It is desired to increase the volumetric energy density of hydrogen in a system to satisfy various applications. Research on hydrogen storage has been pursed for many years. Various storage technologies, including liquefaction, compression, metal hydride, chemical hydride, and adsorption, have been examined. Liquefaction and high pressure compression are not desired due to concerns related to complicated devices, high energy cost and safety. Metal hydrides and chemical hydrides have high gravimetric and volumetric energy densities but encounter issues because high temperature is required for the release of hydrogen, due to the strong bonding of hydrogen in the compounds. Reversibility of hydrogen loading and unloading is another concern. Adsorption of hydrogen on high surface area sorbents such as activated carbon and organic metal frameworks does not have the reversibility problem. But on the other hand, the weak force (primarily the van der Waals force) between hydrogen and the sorbent yields a very small amount of adsorption capacity at ambient temperature. Significant storage capacity can only be achieved at low temperatures such as 77K. The use of liquid nitrogen in a hydrogen storage system is not practical. Perhydrides are proposed as novel hydrogen storage materials that may overcome barriers slowing advances to a hydrogen fuel economy. In conventional hydrides, e.g. metal hydrides, the number of hydrogen atoms equals the total valence of the metal ions. One Li

  19. Hydrogen evolution by a metal-free electrocatalyst

    KAUST Repository

    Zheng, Yao

    2014-04-28

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics. © 2014 Macmillan Publishers Limited. All rights reserved.

  20. 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.

  1. Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

    Science.gov (United States)

    Xiao, Qing; Zhang, Yan; Wang, Jianbo

    2013-02-19

    Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo

  2. Metallic hydrogen: The most powerful rocket fuel yet to exist

    Energy Technology Data Exchange (ETDEWEB)

    Silvera, Isaac F [Lyman Laboratory of Physics, Harvard University, Cambridge MA 02138 (United States); Cole, John W, E-mail: silvera@physics.harvard.ed [NASA MSFC, Huntsville, AL 35801 (United States)

    2010-03-01

    Wigner and Huntington first predicted that pressures of order 25 GPa were required for the transition of solid molecular hydrogen to the atomic metallic phase. Later it was predicted that metallic hydrogen might be a metastable material so that it remains metallic when pressure is released. Experimental pressures achieved on hydrogen have been more than an order of magnitude higher than the predicted transition pressure and yet it remains an insulator. We discuss the applications of metastable metallic hydrogen to rocketry. Metastable metallic hydrogen would be a very light-weight, low volume, powerful rocket propellant. One of the characteristics of a propellant is its specific impulse, I{sub sp}. Liquid (molecular) hydrogen-oxygen used in modern rockets has an Isp of {approx}460s; metallic hydrogen has a theoretical I{sub sp} of 1700s. Detailed analysis shows that such a fuel would allow single-stage rockets to enter into orbit or carry economical payloads to the moon. If pure metallic hydrogen is used as a propellant, the reaction chamber temperature is calculated to be greater than 6000 K, too high for currently known rocket engine materials. By diluting metallic hydrogen with liquid hydrogen or water, the reaction temperature can be reduced, yet there is still a significant performance improvement for the diluted mixture.

  3. Zinc oxide and chromia as catalysts for the isomerization of butene, the hydrogenation of ethylene, and the isotopic exchange and allotropic conversion of hydrogen

    International Nuclear Information System (INIS)

    Conner, W.C. Jr.

    1973-01-01

    Hydrogenation of olefins has been studied over metals and metal oxides. Over metals the following observations generalize the characteristics of hydrogenation and isomerization. Metal hydrogenation catalysts are effective for H 2 -D 2 exchange (and para hydrogen conversion) under the same conditions as they effect olefin hydrogenation. This suggests that hydrogen ''activation'' involves formation of hydrogen atoms as a surface intermediate. Addition of deuterium to light ethylene leads to ethane products of the form C 2 H/sub 6-x/D/sub x/ (where 0 less than or equal to x less than or equal to 6). This is a result of the reversal of the alkyl (C 2 H 5 *) formation on the surface. Moreover, efficient isomerization of olefins require hydrogen as a co-catalyst. Both these observations suggest that alkyl formation and its reversal play a major role in hydrogenation and related reactions over metals. In this work it is found that zinc oxide catalyzes the deuteration of ethylene to dideuterioethane selectivity. Furthermore, the hydrogenation of ethylene using mixtures of hydrogen and deuterium indicate that hydrogenation occurs in such a manner as to reflect the molecular identity of the gas phase in the product ethane

  4. Metallic Hydrogen: A Game Changing Rocket Propellant

    Science.gov (United States)

    Silvera, Isaac F.

    2016-01-01

    The objective of this research is to produce metallic hydrogen in the laboratory using an innovative approach, and to study its metastability properties. Current theoretical and experimental considerations expect that extremely high pressures of order 4-6 megabar are required to transform molecular hydrogen to the metallic phase. When metallic hydrogen is produced in the laboratory it will be extremely important to determine if it is metastable at modest temperatures, i.e. remains metallic when the pressure is released. Then it could be used as the most powerful chemical rocket fuel that exists and revolutionize rocketry, allowing single-stage rockets to enter orbit and chemically fueled rockets to explore our solar system.

  5. Hydrogen in metals

    International Nuclear Information System (INIS)

    1986-01-01

    The report briefly describes the results of the single projects promoted by the German Council of Research (DFG). The subjects deal with diffusion, effusion, permeation and solubility of hydrogen in metals. They are interesting for many disciplines: metallurgy, physical metallurgy, metal physics, materials testing, welding engineering, chemistry, nuclear physics and solid-state physics. The research projects deal with the following interrelated subjects: solubility of H 2 in steel and effects on embrittlement, influence of H 2 on the fatigue strength of steel as well as the effect of H 2 on welded joints. The studies in solid-state research can be divided into methodological and physico-chemical studies. The methodological studies mainly comprise investigations on the analytical determination of H 2 by means of nuclear-physical reactions (e.g. the 15 N method) and the application of the Moessbauer spectroscopy. Physico-chemical problems are mainly dealt with in studies on interfacial reactions in connection with the absorption of hydrogen and on the diffusion of H 2 in different alloy systems. The properties of materials used for hydrogen storage were the subject of several research projects. 20 contributions were separately recorded for the data bank 'Energy'. (MM) [de

  6. Beckmann rearrangement of aldoximes catalyzed by transition metal salts: mechanical aspects

    NARCIS (Netherlands)

    Leusink, A.J.; Meerbeek, T.G.; Noltes, J.G.

    1977-01-01

    The Beckmann rearrangement of aldoximes catalyzed by transition metal salts like palladium and nickel acetylacetonates is shown to be a dehydration‐hydration reaction in which the anti‐oxime is converted into nitrile and the nitrile is converted into amide.

  7. Conversion of cellulose and cellobiose into sorbitol catalyzed by ruthenium supported on a polyoxometalate/metal-organic framework hybrid.

    Science.gov (United States)

    Chen, Jinzhu; Wang, Shengpei; Huang, Jing; Chen, Limin; Ma, Longlong; Huang, Xing

    2013-08-01

    Cellulose and cellobiose were selectively converted into sorbitol over water-tolerant phosphotungstic acid (PTA)/metal- organic-framework-hybrid-supported ruthenium catalysts, Ru-PTA/MIL-100(Cr), under aqueous hydrogenation conditions. The goal was to investigate the relationship between the acid/metal balance of bifunctional catalysts Ru-PTA/MIL-100(Cr) and their performance in the catalytic conversion of cellulose and cellobiose into sugar alcohols. The control of the amount and strength of acid sites in the supported PTA/MIL-100(Cr) was achieved through the effective control of encapsulated-PTA loading in MIL-100(Cr). This design and preparation method led to an appropriately balanced Ru-PTA/MIL-100(Cr) in terms of Ru dispersion and hydrogenation capacity on the one hand, and acid site density of PTA/MIL-100(Cr) (responsible for acid-catalyzed hydrolysis) on the other hand. The ratio of acid site density to the number of Ru surface atoms (nA /nRu ) of Ru-PTA/MIL-100(Cr) was used to monitor the balance between hydrogenation and hydrolysis functions; the optimum balance between the two catalytic functions, that is, 8.84sorbitol of 57.9% at complete conversion of cellulose, and 97.1% yield in hexitols with a selectivity for sorbitol of 95.1% at complete conversion of cellobiose) were obtained using a Ru-PTA/MIL-100(Cr) catalyst with loadings of 3.2 wt % for Ru and 16.7 wt % for PTA. This research thus opens new perspectives for the rational design of acid/metal bifunctional catalysts for biomass conversion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Aluminum-catalyzed silicon nanowires: Growth methods, properties, and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hainey, Mel F.; Redwing, Joan M. [Department of Materials Science and Engineering, Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2016-12-15

    Metal-mediated vapor-liquid-solid (VLS) growth is a promising approach for the fabrication of silicon nanowires, although residual metal incorporation into the nanowires during growth can adversely impact electronic properties particularly when metals such as gold and copper are utilized. Aluminum, which acts as a shallow acceptor in silicon, is therefore of significant interest for the growth of p-type silicon nanowires but has presented challenges due to its propensity for oxidation. This paper summarizes the key aspects of aluminum-catalyzed nanowire growth along with wire properties and device results. In the first section, aluminum-catalyzed nanowire growth is discussed with a specific emphasis on methods to mitigate aluminum oxide formation. Next, the influence of growth parameters such as growth temperature, precursor partial pressure, and hydrogen partial pressure on nanowire morphology is discussed, followed by a brief review of the growth of templated and patterned arrays of nanowires. Aluminum incorporation into the nanowires is then discussed in detail, including measurements of the aluminum concentration within wires using atom probe tomography and assessment of electrical properties by four point resistance measurements. Finally, the use of aluminum-catalyzed VLS growth for device fabrication is reviewed including results on single-wire radial p-n junction solar cells and planar solar cells fabricated with nanowire/nanopyramid texturing.

  9. Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

    Science.gov (United States)

    Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

    2015-12-21

    Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

  11. Hydrogen embrittlement and stress corrosion cracking in metals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Cheong, Yong Mu; Im, Kyung Soo

    2004-10-15

    The objective of this report is to elucidate the mechanism for hydrogen embrittlement (HE) and stress corrosion cracking (SCC) in metals. To this end, we investigate the common features between delayed hydride cracking (DHC) in zirconium alloys and HE in metals with no precipitation of hydrides including Fe base alloys, Nickel base alloys, Cu alloys and Al alloys. Surprisingly, as with the crack growth pattern for the DHC in zirconium alloy, the metals mentioned above show a discontinuous crack growth, striation lines and a strong dependence of yield strength when exposed to hydrogen internally and externally. This study, for the first time, analyzes the driving force for the HE in metals in viewpoints of Kim's DHC model that a driving force for the DHC in zirconium alloys is a supersaturated hydrogen concentration coming from a hysteresis of the terminal solid solubility of hydrogen, not by the stress gradient, As with the crack growing only along the hydride habit plane during the DHC in zirconium alloys, the metals exposed to hydrogen seem to have the crack growing by invoking the dislocation slip along the preferential planes as a result of some interactions of the dislocations with hydrogen. Therefore, it seems that the hydrogen plays a role in inducing the slip only on the preferential planes so as to cause a strain localization at the crack tip. Sulfur in metals is detrimental in causing a intergranular cracking due to a segregation of the hydrogens at the grain boundaries. In contrast, boron in excess of 500 ppm added to the Ni3Al intermetallic compound is found to be beneficial in suppressing the HE even though further details of the mechanism for the roles of boron and sulfur are required. Carbon, carbides precipitating semi-continuously along the grain boundaries and the CSL (coherent site lattice) boundaries is found to suppress the intergranular stress corrosion cracking (IGSCC) in Alloy 600. The higher the volume fraction of twin boundaries, the

  12. Hydrogen embrittlement and stress corrosion cracking in metals

    International Nuclear Information System (INIS)

    Kim, Young Suk; Cheong, Yong Mu; Im, Kyung Soo

    2004-10-01

    The objective of this report is to elucidate the mechanism for hydrogen embrittlement (HE) and stress corrosion cracking (SCC) in metals. To this end, we investigate the common features between delayed hydride cracking (DHC) in zirconium alloys and HE in metals with no precipitation of hydrides including Fe base alloys, Nickel base alloys, Cu alloys and Al alloys. Surprisingly, as with the crack growth pattern for the DHC in zirconium alloy, the metals mentioned above show a discontinuous crack growth, striation lines and a strong dependence of yield strength when exposed to hydrogen internally and externally. This study, for the first time, analyzes the driving force for the HE in metals in viewpoints of Kim's DHC model that a driving force for the DHC in zirconium alloys is a supersaturated hydrogen concentration coming from a hysteresis of the terminal solid solubility of hydrogen, not by the stress gradient, As with the crack growing only along the hydride habit plane during the DHC in zirconium alloys, the metals exposed to hydrogen seem to have the crack growing by invoking the dislocation slip along the preferential planes as a result of some interactions of the dislocations with hydrogen. Therefore, it seems that the hydrogen plays a role in inducing the slip only on the preferential planes so as to cause a strain localization at the crack tip. Sulfur in metals is detrimental in causing a intergranular cracking due to a segregation of the hydrogens at the grain boundaries. In contrast, boron in excess of 500 ppm added to the Ni3Al intermetallic compound is found to be beneficial in suppressing the HE even though further details of the mechanism for the roles of boron and sulfur are required. Carbon, carbides precipitating semi-continuously along the grain boundaries and the CSL (coherent site lattice) boundaries is found to suppress the intergranular stress corrosion cracking (IGSCC) in Alloy 600. The higher the volume fraction of twin boundaries, the more

  13. Liquid Metallic Hydrogen: A Building Block for the Liquid Sun

    Directory of Open Access Journals (Sweden)

    Robitaille P.-M.

    2011-07-01

    Full Text Available Liquid metallic hydrogen provides a compelling material for constructing a condensed matter model of the Sun and the photosphere. Like diamond, metallic hydrogen might have the potential to be a metastable substance requiring high pressures for forma- tion. Once created, it would remain stable even at lower pressures. The metallic form of hydrogen was initially conceived in 1935 by Eugene Wigner and Hillard B. Huntington who indirectly anticipated its elevated critical temperature for liquefaction (Wigner E. and Huntington H.B. On the possibility of a metallic modification of hydro- gen. J. Chem. Phys. , 1935, v.3, 764–770. At that time, solid metallic hydrogen was hypothesized to exist as a body centered cubic, although a more energetically accessible layered graphite-like lattice was also envisioned. Relative to solar emission, this struc- tural resemblance between graphite and layered metallic hydrogen should not be easily dismissed. In the laboratory, metallic hydrogen remains an elusive material. However, given the extensive observational evidence for a condensed Sun composed primarily of hydrogen, it is appropriate to consider metallic hydrogen as a solar building block. It is anticipated that solar liquid metallic hydrogen should possess at least some layered order. Since layered liquid metallic hydrogen would be essentially incompressible, its invocation as a solar constituent brings into question much of current stellar physics. The central proof of a liquid state remains the thermal spectrum of the Sun itself. Its proper understanding brings together all the great forces which shaped modern physics. Although other proofs exist for a liquid photosphere, our focus remains solidly on the generation of this light.

  14. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  15. Hydrogen-induced high damping of bulk metallic glasses

    International Nuclear Information System (INIS)

    Hasegawa, M.

    2009-01-01

    There are two important topics concerned with the recent researches on the damping materials of hydrogenated metallic glasses (HMGs). One is the mechanism of the high hydrogen-induced internal friction of HMGs. The other is the materials processing of 'bulk' HMGs for engineering. This article describes the summary of our recent studies on these topics. The first one is closely related to the local structure of the metallic glasses. Therefore, our recent results on the intermediate-range local structure of the simple two Zr-based metallic glasses are described, which has been clarified by the Voronoi analysis using the experimental data of the neutron diffraction measurements. The hydrogen-induced internal friction of HMGs is also discussed on the basis of these recent results of the local structure of the metallic glasses. In terms of the second topic, the first successful preparation of heavily hydrogenated Zr-based bulk HMG rods without hydrogen-induced surface embrittlement is described. They are prepared by a powder-compact-melting and liquid-casting process using Zr-Al-Ni-Cu metallic glass and ZrH 2 powders as the starting materials. It has been found that they have high damping properties.

  16. Hydrogen as a New Alloying Element in Metals

    International Nuclear Information System (INIS)

    Shapovalov, Vladimir

    1999-01-01

    Hydrogen was regarded as a harmful impurity in many alloys and particularly in steels where it gives rise to a specific type of embrittlement and forms various discontinuities like flakes and blowholes. For this reason, the researcher efforts were mainly focused on eliminating hydrogen's negative impacts and explaining its uncommonly high diffusivity in condensed phases. Meanwhile, positive characteristics of hydrogen as an alloying element remained unknown for quite a long time. Initial reports in this field did not appear before the early 1970s. Data on new phase diagrams are given for metal-hydrogen systems where the metal may or may not form hydrides. Various kinds of hydrogen impact on structure formation in solidification, melting and solid-solid transformations are covered. Special attention is given to the most popular alloys based on iron, aluminum, copper, nickel, magnesium and titanium. Detailed is what is called gas-eutectic reaction resulting in a special type of gas-solid structure named gasarite. Properties and applications of gasars - gasaritic porous materials - are dealt with. Various versions of solid-state alloying with hydrogen are discussed that change physical properties and fabrication characteristics of metals. Details are given on a unique phenomenon of anomalous spontaneous deformation due to combination of hydrogen environment and polymorphic transformation. All currently known versions of alloying with hydrogen are categorized for both hydride-forming and non-hydrid forming metals

  17. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Long, Jeffrey R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  18. Reactor prospects of muon-catalyzed fusion of deuterium and tritium concentrated in transition metals

    International Nuclear Information System (INIS)

    Stacey, W.M. Jr.

    1989-01-01

    It is conjectured that the number of fusion events catalyzed by a single muon is orders of magnitude greater for deuterium and tritium concentrated in a transition metal than in gaseous form and that the recent observation of 2.5-MeV neutrons from a D 2 O electrolytic cell with palladium and titanium cathodes can thereby be interpreted in terms of cosmic muon-catalyzed deuterium-deuterium fusion. This suggests a new fusion reactor reactor consisting of deuterium and tritium concentrated in transition metal fuel elements in a fusion core that surrounds an accelerator-produced muon source. The feasibility of net energy production in such a reactor is established in terms of requirements on the number of fusion events catalyzed per muon. The technological implications for a power reactor based on this concept are examined. The potential of such a concept as a neutron source for materials testing and tritium and plutonium production is briefly discussed

  19. Microporous Metal Organic Materials for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  20. Metal ammine complexes for hydrogen storage

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Sørensen, Rasmus Zink; Johannessen, Tue

    2005-01-01

    The hopes of using hydrogen as an energy carrier are severely dampened by the fact that there is still no safe, high-density method available for storing hydrogen. We investigate the possibility of using metal ammine complexes as a solid form of hydrogen storage. Using Mg(NH3)(6)Cl-2 as the example......, we show that it can store 9.1% hydrogen by weight in the form of ammonia. The storage is completely reversible, and by combining it with an ammonia decomposition catalyst, hydrogen can be delivered at temperatures below 620 K....

  1. An iron/amine-catalyzed cascade process for the enantioselective functionalization of allylic alcohols.

    Science.gov (United States)

    Quintard, Adrien; Constantieux, Thierry; Rodriguez, Jean

    2013-12-02

    Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Metal-support interactions in electrocatalysis: Hydrogen effects on electron and hole transport at metal-support contacts

    International Nuclear Information System (INIS)

    Heller, A.

    1986-01-01

    This paper discusses the effects of hydrogen on electron and hole transport at metal support contacts during electrocatalysis. When hydrogen dissolves in high work function metals such as Pt, Rh or Ru the contact forms between the semiconductor and the hydrogenated metal, which has a work function that is lower than that of the pure metal. Thus by changing the gaseous atmosphere that envelopes metal-substrate contacts, it is possible to reversibly change their diode characteristics. In some cases, such as Pt on n-TiO/sub 2/, Rh on n-TiO/sub 2/ and Ru on n-TiO/sub 2/, it is even possible to reversibly convert Schottky diodes into ohmic contacts by changing the atmosphere from air to hydrogen. In contacts between hydrogen dissolving group VIII metals and semiconducting substrates, one can test for interfacial reaction of the catalysts and the substrate by examining the electrical characteristics of the contacts in air (oxygen) and in hydrogen. In the absence of interfacial reaction, large hydrogen induced variation in the barrier heights is observed and the hydrogenated contacts, approach ideality (i.e. their non-ideality factor is close to unity). When a group VIII metal and a substrate do react, the reaction often produces a phase that blocks hydrogen transport to the interface between the substrate and the reaction product. In this case the hydrogen effect is reduced or absent. Furthermore, because such reaction often introduces defects into the surface of the semiconductor, the contacts have non-ideal diode characteristics

  3. Interaction of hydrogen and oxygen with bulk defects and surfaces of metals

    International Nuclear Information System (INIS)

    Besenbacher, F.

    1994-05-01

    The thesis deals with the interaction of hydrogen with defects in metals and the interaction of hydrogen and oxygen with metal surfaces studied by ion-beam techniques and scanning tunneling microscopy (STM), respectively. The first part of the thesis discusses the interaction of hydrogen with simple defects in transition metals. The trap-binding enthalpies and the lattice location of hydrogen trapped to vacancies have been determined, and an extremely simple and versatile picture of the hydrogen-metal interaction has evolved, in which the trap strength is mainly determined by the local electron density. Any dilution of the lattice will lead to a trap, vacancies and voids being the strongest trap. It is found that hydrogen trapped to vacancies in fcc metals is quantum-mechanically delocalized, and the excitation energies for the hydrogen in the vacancy potential are a few MeV only. The interaction of hydrogen with metal surfaces is studied by the transmission channeling (TC) technique. It is found that hydrogen chemisorbs in the highest-coordinated sites on the surfaces, and that there is a direct relationship between the hydrogen-metal bond length and the coordination number for the hydrogen. In the final part of the thesis the dynamics of the chemisorption process for oxygen and hydrogen on metal surfaces is studied by STM, a fascinating and powerful technique for exploring the atomic-scale realm of surfaces. It is found that there is a strong coupling between the chemisorption process and the distortion of the metal surface. The adsorbates induce a surface reconstruction, i.e. metal-metal bond breaks and metal-adsorbate bounds form. Whereas hydrogen interacts weakly with the metals and induces reconstructions where only nnn metals bonds are broken, oxygen interacts strongly with the metal, and the driving force for the O-induced reconstructions appears to be the formation of low-coordinated metal-O rows, formed by breaking of nn metal bonds. Finally it is shown

  4. Hydrogen storage properties of metallic hydrides

    International Nuclear Information System (INIS)

    Latroche, M.; Percheron-Guegan, A.

    2005-01-01

    Nowadays, energy needs are mainly covered by fossil energies leading to pollutant emissions mostly responsible for global warming. Among the different possible solutions for greenhouse effect reduction, hydrogen has been proposed for energy transportation. Indeed, H 2 can be seen as a clean and efficient energy carrier. However, beside the difficulties related to hydrogen production, efficient high capacity storage means are still to be developed. Many metals and alloys are able to store large amounts of hydrogen. This latter solution is of interest in terms of safety, global yield and long term storage. However, to be suitable for applications, such compounds must present high capacity, good reversibility, fast reactivity and sustainability. In this paper, we will review the structural and thermodynamic properties of metallic hydrides. (authors)

  5. Theoretical study of hydrogen storage in metal hydrides.

    Science.gov (United States)

    Oliveira, Alyson C M; Pavão, A C

    2018-05-04

    Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

  6. Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

    International Nuclear Information System (INIS)

    Britton, M.D.

    1995-01-01

    This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

  7. Metal oxide/hydrogen battery; Kinzoku sankabutsu/suiso denchi

    Energy Technology Data Exchange (ETDEWEB)

    Kanda, M.; Niki, H. [Toshiba Research and Development Centre, Komukai, Kawasaki (Japan)

    1995-07-04

    The metal oxide-hydrogen battery consisting mainly of hydrogen storage alloy has high energy density and high volume efficiency. However, it is disadvantageous that the self-discharge takes place since the discharge capacity is lowered due to the delivery of stored hydrogen from the hydrogen electrode. This invention relates to the metal oxide-hydrogen battery consisting of hydrogen storage alloy. Hydrogen storage alloy which is composed of LaNi5 system homogeneous solid solution having an equilibrium plateau pressure of less than 1 atm at 20{degree}C is used. As a result, the battery voltage change and the self-discharge can be reduced, and the cell performance can be improved. Examples of LaNi5 system hydrogen storage alloy are ANi(5-x)Mx (A = La, Mm, and Ca, M = Al, Mn, Si, Ge, Fe, B, Ga, Cu, In, and Co). LaNi(4.7)Al(0.3) and MmNi(4.2)Mn(0.8) are preferable. 3 figs.

  8. Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

    International Nuclear Information System (INIS)

    Lee, Hyung Soo; Lee, Gab Yong

    2005-01-01

    The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

  9. Gold Supported on Graphene Oxide: An Active and Selective Catalyst for Phenylacetylene Hydrogenations at Low Temperatures

    DEFF Research Database (Denmark)

    Shao, Lidong; Huang, Xing; Teschner, Detre

    2014-01-01

    A constraint to industrial implementation of gold-catalyzed alkyne hydrogenation is that the catalytic activity was always inferior to those of other noble metals. In this work, gold was supported on graphene oxide (Au/GO) and used in a hydrogenation application. A 99% selectivity toward styrene...

  10. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.

    1992-04-07

    The ultimate objective of this research has been to uncover novel reagents and experimental conditions for heteroatom removal and hydrogen transfer processes, which would be applicable to the liquefaction of coal under low-severity conditions. To this end, one phase of this research has investigated the cleavage of carbon-heteroatom bonds involving sulfur, oxygen, nitrogen and halogen by subvalent transition-metal complexes. A second phase of the study has assessed the capability of the same transition-metal complexes or of organoaluminum Lewis acids to catalyze the cleavage of carbon-hydrogen bonds in aromatics and hence to promote hydrogen shuttling. Finally, a third phase of our work has uncovered a remarkable synergistic effect of combinations of transition metals with organoaluminum Lewis acids on hydrogen shuttling between aromatics and hydroaromatics. (VC)

  11. [Effects of metal-catalyzed oxidation on the formation of advanced oxidation protein products].

    Science.gov (United States)

    Li, Li; Peng, Ai; Zhu, Kai-Yuan; Yu, Hong; Ll, Xin-Hua; Li, Chang-Bin

    2008-03-11

    To explore the relationship between metal-catalyzed oxidation (MCO) and the formation of advanced oxidation protein products (AOPPs). Specimens of human serum albumin (HSA) and pooled plasma were collected from 3 healthy volunteers and 4 uremia patients were divided into 3 groups: Group A incubated with copper sulfate solution of the concentrations of 0, 0.2, or 0.5 mmol/L, Group B, incubated with hydrogen peroxide 2 mmol/L, and Group C, incubated with copper sulfate 0.2 or 0.5 mmol/L plus hydrogen peroxide 2 mmol/L. 30 min and 24 h later the AOPP level was determined by ultraviolet visible spectrophotometry. High-performance liquid chromatography (HPLC) was used to observe the fragmentation effect on plasma proteins. Ninhydrin method was used to examine the protein fragments. The scavenging capacity of hydroxyl radical by macromolecules was measured so as to estimate the extent of damage for proteins induced by MCO. (1) The AOPP level of the HSA and plasma specimens of the uremia patients increased along with the increase of cupric ion concentration in a dose-dependent manner, especially in the presence of hydrogen peroxide (P < 0.05). (2) Aggregation of proteins was almost negligible in all groups, however, HPLC showed that cupric ion with or without hydrogen peroxide increased the fragments in the HAS specimens (with a relative molecular mass of 5000) and uremia patients' plasma proteins (with the molecular mass 7000). (3) The plasma AOPP level of the healthy volunteers was 68.2 micromol/L +/- 2.4 micromol/L, significantly lower than that of the uremia patients (158.5 micromol/L +/- 8.2 micromol/L). (4) The scavenging ability to clear hydroxyl radical by plasma proteins of the healthy volunteers was 1.38 -9.03 times as higher than that of the uremia patients. MCO contributes to the formation of AOPPs mainly through its fragmentation effect to proteins.

  12. Hydrogen adsorption in metal-decorated silicon carbide nanotubes

    Science.gov (United States)

    Singh, Ram Sevak; Solanki, Ankit

    2016-09-01

    Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

  13. Interaction of hydrogen with metallic nanojunctions

    Energy Technology Data Exchange (ETDEWEB)

    Halbritter, Andras; Csonka, Szabolcs; Makk, Peter; Mihaly, Gyoergy [Electron Transport Research Group of the Hungarian Academy of Sciences and Department of Physics, Budapest University of Technology and Economics, 1111 Budapest (Hungary)

    2007-03-15

    We study the behavior of hydrogen molecules between atomic-sized metallic electrodes using the mechanically controllable break junction technique. We focus on the interaction H{sub 2} with monoatomic gold chains demonstrating the possibility of a hydrogen molecule being incorporated in the chain. We also show that niobium is strongly reactive with hydrogen, which enables molecular transport studies between superconducting electrodes. This opens the possibility for a full characterization of the transmission properties of molecular junctions with superconducting subgap structure measurements.

  14. Noble metal-catalyzed homogeneous and heterogeneous processes in treating simulated nuclear waste media with formic acid

    International Nuclear Information System (INIS)

    King, R.B.; Bhattacharyya, N.K.; Smith, H.D.

    1995-09-01

    Simulants for the Hanford Waste Vitrification Plant feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2 -, NO 3 -, and NO 2 - were used to study reactions of formic acid at 90 degrees C catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Such reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase and a microammonia electrode to analyze the NH 4 +/NH 3 in the liquid phase as a function of time. The following reactions have been studied in these systems since they are undesirable side reactions in nuclear waste processing: (1) Decomposition of formic acid to CO 2 + H 2 is undesirable because of the potential fire and explosion hazard of H 2 . Rhodium, which was introduced as soluble RhCl 3 -3H 2 O, was found to be the most active catalyst for H 2 generation from formic acid above ∼ 80 degrees C in the presence of nitrite ion. The H 2 production rate has an approximate pseudo first-order dependence on the Rh concentration, (2) Generation of NH 3 from the formic acid reduction of nitrate and/or nitrite is undesirable because of a possible explosion hazard from NH 4 NO 3 accumulation in a waste processing plant off-gas system. The Rh-catalyzed reduction of nitrogen-oxygen compounds to ammonia by formic acid was found to exhibit the following features: (a) Nitrate rather than nitrite is the principal source of NH 3 . (b) Ammonia production occurs at the expense of hydrogen production. (c) Supported rhodium metal catalysts are more active than rhodium in any other form, suggesting that ammonia production involves heterogeneous rather than homogeneous catalysis

  15. Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

    Directory of Open Access Journals (Sweden)

    Kei Murakami

    2013-02-01

    Full Text Available Carbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon–carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1 alkynes bearing an electron-withdrawing group; (2 alkynes bearing a directing group; (3 strained cyclopropenes; (4 unactivated alkynes or alkenes; and (5 substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes.

  16. Adsorption of hydrogen isotopes by metals in non-equilibrium conditions

    International Nuclear Information System (INIS)

    Livshits, A.I.; Notkin, M.E.; Pustovojt, Yu.M.

    1982-01-01

    To study the interaction of thermonuclear plasma and additions with metallic walls, nonequilibrium system of thermal atomary hydrogen - ''cold'' (300-1100 K) metal is experimentally investigated. Atomary hydrogen was feeded to samples of Ni and Pd in the shape of atomic beam, coming into vacuum from high-frequency gaseous discharge. It is shown that hydrogen solubility under nonequilibrium conditions increases with surface passivation (contamination); in this case it surpasses equilibrium solubility by value orders. Nickel and iron dissolve more hydrogen than palladium at a certain state of surface ( passivation) and gas (atomary hydrogen). The sign of the temperature dependence of hydrogen solubility in passivated N 1 and Fe changes when alterating molecular hydrogen by atomary hydrogen

  17. Hydrogen storage evaluation based on investigations of the catalytic properties of metal/metal oxides in electrospun carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

    Im, Ji Sun; Lee, Young-Seak [Department of Fine Chemical Engineering and Chemistry, Chungnam National University, Daejeon 305-764 (Korea); Park, Soo-Jin [Department of Chemistry, Inha University, Incheon 402-751 (Korea); Kim, Taejin [Core Technology Research Center for Fuel Cell, Jeollabuk-do 561-844 (Korea)

    2009-05-15

    In order to investigate the catalytic capacity of metals and metal oxides based on electrospun carbon fibers for improving hydrogen storage, electrospinning and heat treatments were carried out to obtain metal/metal oxide-embedded carbon fibers. Although the fibers were treated with the same activation procedure, they had different pore structures, due to the nature of the metal oxide. When comparing the catalytic capacity of metal and metal oxide, metal exhibits better performance as a catalyst for the improvement of hydrogen storage, when considering the hydrogen storage system. When a metal oxide with an m.p. lower than the temperature of heat treatment was used, the metal oxide was changed to metal during the heat treatment, developing a micropore structure. The activation process produced a high specific surface area of up to 2900 m{sup 2}/g and a pore volume of up to 2.5 cc/g. The amount of hydrogen adsorption reached approximately 3 wt% at 100 bar and room temperature. (author)

  18. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  19. Towards hydrogen metallization: an Ab initio approach; Vers la metallisation de l`hydrogene: approche AB initio

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, St

    1998-12-31

    The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H{sub 2}){sub 2} which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author) 109 refs.

  20. Towards hydrogen metallization: an Ab initio approach; Vers la metallisation de l`hydrogene: approche AB initio

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, St

    1999-12-31

    The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H{sub 2}){sub 2} which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author) 109 refs.

  1. Hydrogen release at metal-oxide interfaces: A first principle study of hydrogenated Al/SiO{sub 2} interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jianqiu, E-mail: jianqiu@vt.edu [Department of Mechanical Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road - MC 0238, Blacksburg, VA 24061 (United States); Tea, Eric; Li, Guanchen [Department of Mechanical Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road - MC 0238, Blacksburg, VA 24061 (United States); Hin, Celine [Department of Mechanical Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road - MC 0238, Blacksburg, VA 24061 (United States); Department of Material Science and Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road-MC 0238, Blacksburg, VA 24061 (United States)

    2017-06-01

    Highlights: • Hydrogen release process at the Al/SiO{sub 2} metal-oxide interface has been investigated. • A mathematical model that estimates the hydrogen release potential has been proposed. • Al atoms, Al−O bonds, and Si−Al bonds are the major hydrogen traps at the Al/SiO{sub 2} interface. • Hydrogen atoms are primarily release from Al−H and O−H bonds at the Al/SiO{sub 2} metal-oxide interface. - Abstract: The Anode Hydrogen Release (AHR) mechanism at interfaces is responsible for the generation of defects, that traps charge carriers and can induce dielectric breakdown in Metal-Oxide-Semiconductor Field Effect Transistors. The AHR has been extensively studied at Si/SiO{sub 2} interfaces but its characteristics at metal-silica interfaces remain unclear. In this study, we performed Density Functional Theory (DFT) calculations to study the hydrogen release mechanism at the typical Al/SiO{sub 2} metal-oxide interface. We found that interstitial hydrogen atoms can break interfacial Al−Si bonds, passivating a Si sp{sup 3} orbital. Interstitial hydrogen atoms can also break interfacial Al−O bonds, or be adsorbed at the interface on aluminum, forming stable Al−H−Al bridges. We showed that hydrogenated O−H, Si−H and Al−H bonds at the Al/SiO{sub 2} interfaces are polarized. The resulting bond dipole weakens the O−H and Si−H bonds, but strengthens the Al−H bond under the application of a positive bias at the metal gate. Our calculations indicate that Al−H bonds and O−H bonds are more important than Si−H bonds for the hydrogen release process.

  2. Review of thermodinamic and mechanical properties of hydrogen-transition metal systems

    International Nuclear Information System (INIS)

    Mathias, H.; Katz, Y.

    1978-04-01

    A large body of fundamental and empirical knowledge has been acquired during many years of research concerning the interactions between hydrogen and metals, the location of hydrogen in metal structures, its mobility in metals and its influence on mechanical properties of metals. Much progress has been made in the understanding of related phenomena, and various theories have been proposed, but considerable disagreement still exist about basic mechanisms involved. The growing interest in these subjects and their important role in science and technology are well documented by many reviews and symposia. A general survey of these topics with reference to experimental results and theories related to thermodynamic and mechanical properties of hydrogen-transition metal systems, such as H-Pd, H-Ti, H-Fe etc. is given in the present review. Special emphasis is given to hydrogen embrittlement of metals

  3. Theory of hydrogen chemisorption on metals

    International Nuclear Information System (INIS)

    Brenig, W.

    1975-01-01

    A theory of hydrogen chemisorption on metals is presented. Green's function is derived taking into account the coupling strength between metal and chemisorbed atom and the strength of the interatomic Coulomb repulsion, allowing the calculation of the local density of states at the adatom, especially for the limiting cases of strong and weak coupling

  4. Storage of hydrogen in metals

    International Nuclear Information System (INIS)

    Wiswall, R.

    1981-01-01

    A review is dedicated to a problem of hydrogen storage as fuel of future, that can be used under various conditions, is easily obtained with the help of other types of energy and can be transformed into them. Data on reversible metal-hydrogen systems, where hydrogen can be obtained by the way of reaction of thermal decomposition are presented. Pressure-temperature-content diagrams, information on concrete Pd-H, TiFe-H, V-N systems are presented and analyzed from the point of view of thermodynamics. A table with thermodynamical characteristics of several hydrides is presented. The majority of known solid hydrides in relation to their use for hydrogen storage are characterized. The review includes information on real or supposed uses in concrete systems: in fuel cells, for levelling of loading of electric plants, in automobile engines, in hydride engines, for heat storage [ru

  5. Solubility of hydrogen isotopes in stressed hydride-forming metals

    International Nuclear Information System (INIS)

    Coleman, C.E.; Ambler, J.F.R.

    1983-01-01

    Components made from hydride-forming metals can be brittle when particles of hydride are present. The solid solubility limit of hydrogen in these metals needs to be known so that fracture resistance can be properly assessed. Stress affects the solubility of hydrogen in metals. As hydrogen dissolves the metal volume increases, an applied hydrostatic tensile stress supplies work to increase the solubility. Precipitation of hydrides increases the volume further. A hydrostatic tensile stress promotes the formation of hydrides and tends to reduce the terminal solubility. For materials containing hydrogen in solution in equilibrium with hydrides, the effect of stress on the terminal solubility is given. Hydrogen migrates up tensile stress gradients because of the effect of stress on the solubility and solubility limit. Consequently, hydrogen concentrates at flaws. When hydrides are present in the metal matrix, those remote from the flaw tip will preferentially dissolve in favor of those precipitated at the flaw. If the stress is large enough, at some critical condition the hydrides at the flaw will crack. This is delayed hydrogen cracking. Notched and fatigue-cracked cantilever beam specimens (6) (38 x 4 x 3 mm) were machined from the circumferential direction of several cold-worked Zr-2.5 at. % Nb pressure tubes. The chemical compositions had the ranges (in atomic %) Nb - 2.5 to 2.7; O - 0.58 to 0.71; H - 0.018 to 0.18. The effect of test temperature is for a specimen containing 0.13 at. % protium and 0.29 at .% deuterium. Between 505 K and 530 K was less than 1 hr, between 530 K and 537 K it increased to 25.8 h, while at 538 K no cracking was observed up to the 54 h

  6. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

    2011-01-01

    Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

  7. Carrier gas effects on aluminum-catalyzed nanowire growth

    International Nuclear Information System (INIS)

    Ke, Yue; Hainey, Mel Jr; Won, Dongjin; Weng, Xiaojun; Eichfeld, Sarah M; Redwing, Joan M

    2016-01-01

    Aluminum-catalyzed silicon nanowire growth under low-pressure chemical vapor deposition conditions requires higher reactor pressures than gold-catalyzed growth, but the reasons for this difference are not well understood. In this study, the effects of reactor pressure and hydrogen partial pressure on silicon nanowire growth using an aluminum catalyst were studied by growing nanowires in hydrogen and hydrogen/nitrogen carrier gas mixtures at different total reactor pressures. Nanowires grown in the nitrogen/hydrogen mixture have faceted catalyst droplet tips, minimal evidence of aluminum diffusion from the tip down the nanowire sidewalls, and significant vapor–solid deposition of silicon on the sidewalls. In comparison, wires grown in pure hydrogen show less well-defined tips, evidence of aluminum diffusion down the nanowire sidewalls at increasing reactor pressures and reduced vapor–solid deposition of silicon on the sidewalls. The results are explained in terms of a model wherein the hydrogen partial pressure plays a critical role in aluminum-catalyzed nanowire growth by controlling hydrogen termination of the silicon nanowire sidewalls. For a given reactor pressure, increased hydrogen partial pressures increase the extent of hydrogen termination of the sidewalls which suppresses SiH_4 adsorption thereby reducing vapor–solid deposition of silicon but increases the surface diffusion length of aluminum. Conversely, lower hydrogen partial pressures reduce the hydrogen termination and also increase the extent of SiH_4 gas phase decomposition, shifting the nanowire growth window to lower growth temperatures and silane partial pressures. (paper)

  8. Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

    Science.gov (United States)

    Lessing, Paul A [Idaho Falls, ID

    2008-07-22

    An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

  9. Analysis of hydrogen in zirconium metallic

    International Nuclear Information System (INIS)

    Rodrigues, A.N.; Vega Bustillos, J.O.W.

    1991-02-01

    Determination of hydrogen in zirconium metallic have been performed using the hot vacuum extraction system and the gas chromatographic technique. The zirconium metallic samples were hydrieded by electrolitic technique at difference temperatures and times, then the samples were annealing at vacuum and eatching by fluoridric acid solution. The details of the hydrieded process, analytical technique and the data obtained are discussed. (author)

  10. Iodine-catalyzed diazo activation to access radical reactivity.

    Science.gov (United States)

    Li, Pan; Zhao, Jingjing; Shi, Lijun; Wang, Jin; Shi, Xiaodong; Li, Fuwei

    2018-05-17

    Transition-metal-catalyzed diazo activation is a classical way to generate metal carbene, which are valuable intermediates in synthetic organic chemistry. An alternative iodine-catalyzed diazo activation is disclosed herein under either photo-initiated or thermal-initiated conditions, which represents an approach to enable carbene radical reactivity. This metal-free diazo activation strategy were successfully applied into olefin cyclopropanation and epoxidation, and applying this method to pyrrole synthesis under thermal-initiated conditions further demonstrates the unique reactivity using this method over typical metal-catalyzed conditions.

  11. Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

    Science.gov (United States)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2016-04-26

    A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

  12. Solutions to commercializing metal hydride hydrogen storage products

    International Nuclear Information System (INIS)

    Tomlinson, J.J.; Belanger, R.

    2004-01-01

    'Full text:' Whilst the concept of a Hydrogen economy in the broad sense may for some analysts and Fuel Cell technology developers be an ever moving target the use of hydrogen exists and is growing in other markets today. The use of hydrogen is increasing. Who are the users? What are their unique needs? How can they better be served? As the use of hydrogen increases there are things we can do to improve the perception and handling of hydrogen as an industrial gas that will impact the future issues of hydrogen as a fuel thereby assisting the mainstream availability of hydrogen fuel a reality. Factors that will induce change in the way hydrogen is used, handled, transported and stored are the factors to concentrate development efforts on. Other factors include: cost; availability; safety; codes and standards; and regulatory authorities acceptance of new codes and standards. New methods of storage and new devices in which the hydrogen is stored will influence and bring about change and increased use. New innovative products based on Metal Hydride hydrogen storage will address some of the barriers to widely distributed hydrogen as a fuel or energy carrier to which successful fuel cell product commercialization is subject. Palcan has developed innovative products based on it's Rare Earth Metal Hydride alloy. Some of these innovations will aid the distribution of hydrogen as a fuel and offer alternatives to the existing hydrogen user and to the Fuel Cell product developer. An overview of the products and how these products will affect the distribution and use of hydrogen as an industrial gas and fuel is presented. (author)

  13. Hydrogen-bonded intermediates and transition states during spontaneous and acid-catalyzed hydrolysis of the carcinogen (+)-anti-BPDE.

    Science.gov (United States)

    Palenik, Mark C; Rodriguez, Jorge H

    2014-07-07

    Understanding mechanisms of (+)-anti-BPDE detoxification is crucial for combating its mutagenic and potent carcinogenic action. However, energetic-structural correlations of reaction intermediates and transition states during detoxification via hydrolysis are poorly understood. To gain mechanistic insight we have computationally characterized intermediate and transition species associated with spontaneous and general-acid catalyzed hydrolysis of (+)-anti-BPDE. We studied the role of cacodylic acid as a proton donor in the rate limiting step. The computed activation energy (ΔG‡) is in agreement with the experimental value for hydrolysis in a sodium cacodylate buffer. Both types of, spontaneous and acid catalyzed, BPDE hydrolysis can proceed through low-entropy hydrogen bonded intermediates prior to formation of transition states whose energies determine reaction activation barriers and rates.

  14. Studies about interaction of hydrogen isotopes with metals and intermetallic compounds

    International Nuclear Information System (INIS)

    Vasut, F.; Anisoara, P.; Zamfirache, M.

    2003-01-01

    Hydrogen is a non-toxic but highly inflammable gas. Compared to other inflammable gases, its range of inflammability in air is much broader (4-74.5%) but it also vaporizes much more easily. Handling of hydrogen in form of hydrides enhances safety. The interaction of hydrogen with metals and intermetallic compounds is a major field within physical chemistry. Using hydride-forming metals and intermetallic compounds, for example, recovery, purification and storage of heavy isotopes in tritium containing system can solve many problems arising in the nuclear-fuel cycle. The paper presents the thermodynamics and the kinetics between hydrogen and metal or intermetallic compounds. (author)

  15. Interactions of hydrogen isotopes and oxides with metal tubes

    International Nuclear Information System (INIS)

    Longhurst, G. R.; Cleaver, J.

    2008-01-01

    Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results. (authors)

  16. Interactions of hydrogen isotopes and oxides with metal tubes

    Energy Technology Data Exchange (ETDEWEB)

    Longhurst, G. R. [Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415-3860 (United States); Cleaver, J. [Idaho State Univ., 921 South 8th Avenue, Pocatello, ID 83201 (United States)

    2008-07-15

    Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results. (authors)

  17. Interactions of Hydrogen Isotopes and Oxides with Metal Tubes

    International Nuclear Information System (INIS)

    Longhurst, Glen R.

    2008-01-01

    Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results

  18. Texture-geometric deformational effects in some metal-hydrogen systems

    International Nuclear Information System (INIS)

    Spivak, L.V.; Kats, M.Ya.

    1992-01-01

    Possible deformation effects were studied in vanadium, tantalum, niobium, palladium and iron which occurred during electrolytic hydrogenation of specimens preliminarily deformed by torsion and then annealed. Noticeable texture-geometric effects were observed and related to the system tendency to enhance the degree of specimen form symmetry during hydrogenation. The latter was an off-beat realization of Le-Chatelier principle. It was assumed that the nature of deformation effects was connected with one of minimization channels for overall elastic stress fields in metals being hydrogenated. Some distinction was revealed in behaviour of 5a group metal, palladium and iron

  19. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng; Wang, Yuan; Lai, Zhiping; Huang, Kuo-Wei

    2017-01-01

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  20. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng

    2017-05-30

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. First-row transition metal hydrogenation and hydrosilylation catalysts

    Science.gov (United States)

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  3. Two-dimensional metal dichalcogenides and oxides for hydrogen evolution

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Vojvodic, Aleksandra; Thygesen, Kristian Sommer

    2015-01-01

    We explore the possibilities of hydrogen evolution by basal planes of 2D metal dichalcogenides and oxides in the 2H and 1T class of structures using the hydrogen binding energy as a computational activity descriptor. For some groups of systems like the Ti, Zr, and Hf dichalcogenides the hydrogen...

  4. Hydrogen storage in metal-organic frameworks: A review

    CSIR Research Space (South Africa)

    Langmi, Henrietta W

    2014-05-01

    Full Text Available Metal-organic frameworks (MOFs) for hydrogen storage have continued to receive intense interest over the past decade. MOFs are a class of organic-inorganic hybrid crystalline materials consisting of metallic moieties that are linked by strong...

  5. Insulator-metal transition of fluid molecular hydrogen

    International Nuclear Information System (INIS)

    Ross, M.

    1996-01-01

    Dynamically compressed fluid hydrogen shows evidence for metallization at the relatively low pressure of 140 GPa (1.4 Mbar) while experiments on solid hydrogen made in a diamond-anvil cell have failed to detect any evidence for gap closure up to a pressure of 230 GPa (2.3 Mbar). Two possible mechanisms for metal- liclike resistivity are put forward. The first is that as a consequence of the large thermal disorder in the fluid (kT∼0.2 endash 0.3 eV) short-range molecular interactions lead to band tailing that extends the band edge into the gap, resulting in closure at a lower pressure than in the solid. The second mechanism argues that molecular dissociation creates H atoms that behave similar to n-type donors in a heavily doped semiconductor and undergo a nonmetal-metal Mott-type transition. copyright 1996 The American Physical Society

  6. Process chemistry related to hydrogen isotopes

    International Nuclear Information System (INIS)

    Iwasaki, Matae; Ogata, Yukio

    1991-01-01

    Hydrogen isotopes, that is, protium, deuterium and tritium, are all related deeply to energy in engineering region. Deuterium and tritium exist usually as water in extremely thin state. Accordingly, the improvement of the technology for separating these isotopes is a large engineering subject. Further, tritium is radioactive and its half-life period is 12.26 years, therefore, it is desirable to fix it in more stable form besides its confinement in the handling system. As the chemical forms of hydrogen, the molecular hydrogen with highest reactivity, metal hydride, carbon-hydrogen-halogen system compounds, various inorganic hydrides, most stable water and hydroxides are enumerated. The grasping of the behavior from reaction to stable state of these hydrogen compounds and the related materials is the base of process chemistry. The reaction of exchanging isotopes between water and hydrogen on solid catalyzers, the decomposition of ethane halide containing hydrogen, the behavior of water and hydroxides in silicates are reported. The isotope exchange between water and hydrogen is expected to be developed as the process of separating and concentrating hydrogen isotopes. (K.I.) 103 refs

  7. Metal and hydrogen catalysis in isotopic hydrogen exchange in some biologically important heterocyclic compounds

    International Nuclear Information System (INIS)

    Buncel, E.; Joly, H.A.; Jones, J.R.; Onyido, I.

    1989-01-01

    This study reports on the catalytic roles of metal and hydrogen ions in tritium exchange in some heterocyclic substrates which occur as residues in many biologically important molecules. We have found that detritiation of 1-methyl[2- 3 H]imidazole is inhibited by a number of metal ions. As well, inhibition of exchange rates was noted with Ag(I) and Cu(II) for [2- 3 H]thiazole and 1-methyl[8- 3 H]inosine, with Ag(I) for [2- 3 H]benzothiazole, and with Cu(II) for 1-methyl[8- 3 H]guanosine. A complete mechanistic description, which includes the various metal ion-coordinated species generated under the experimental conditions, is presented. The results demonstrate the reactivity order: protonated >> metal-coordinated >> neutral substrates. The differential catalytic effects of metal and hydrogen ions in these processes are discussed in terms of the extent of charge developed on the ligating heteroatom in the reaction intermediate. (author). 13 refs.; 1 fig

  8. Experimental studies on cold fusion and hydrogen-metal

    International Nuclear Information System (INIS)

    Locou, P.

    2007-01-01

    The cold fusion is a nuclear fusion realized in pervading conditions of temperature and pressure. My own process is parallel to that of the team of the University of Los Angeles, but shaped in 1996 within my personal and private Laboratory: A small cylinder in which we replace the air by some deuterium to the gas state in - 33 d egree (the deuterium is some hydrogen with a neutron, which we find in quantity in the sea water). We introduce a crystal there, extremely rare - the property of which is to emit continuously one thousand times dose of successful energy and it during several years without outside pyro, natural excitement - electric - that is it creates an electric field in the slightest change in temperature. We carry then the whole in + 7 d egree, what generates in some seconds a 200 000 volt electric field, an intense enough field to separate the pits of the deuterium of their electrons and to admit them to collide with those of the crystal. There is a fusion of protons between them (positive particles of the pit (core)) and a emission of neutrons, which do not merge. It is this emission which serves for measuring the quantity of energy produced by the fusion (merger). We so managed to produce some energy in unlimited quantity, allowing us to feed our installation with electric current in total autarky, and to reduce so our costs of functioning to divers domains. This crystal is exceptional in its applications and to give it the name would return has to break our current headway: the thorough problem, in this current period of takeover by the financial bodies of the possible patents, brought to us to the biggest caution as regards our results. And, as we look for no outside financing, we do not need to submit ourselves to the requirements lauded by the scientific Community, only our results are strictly estimated. For example we can make estimate our bars or patches of Hydrogen - Metal: a simple spectroscopy in YEW will give as result, only, the element H

  9. Hydrogen Sensors Using Nitride-Based Semiconductor Diodes: The Role of Metal/Semiconductor Interfaces

    Directory of Open Access Journals (Sweden)

    Yoshihiro Irokawa

    2011-01-01

    Full Text Available In this paper, I review my recent results in investigating hydrogen sensors using nitride-based semiconductor diodes, focusing on the interaction mechanism of hydrogen with the devices. Firstly, effects of interfacial modification in the devices on hydrogen detection sensitivity are discussed. Surface defects of GaN under Schottky electrodes do not play a critical role in hydrogen sensing characteristics. However, dielectric layers inserted in metal/semiconductor interfaces are found to cause dramatic changes in hydrogen sensing performance, implying that chemical selectivity to hydrogen could be realized. The capacitance-voltage (C-V characteristics reveal that the work function change in the Schottky metal is not responsible mechanism for hydrogen sensitivity. The interface between the metal and the semiconductor plays a critical role in the interaction of hydrogen with semiconductor devises. Secondly, low-frequency C-V characterization is employed to investigate the interaction mechanism of hydrogen with diodes. As a result, it is suggested that the formation of a metal/semiconductor interfacial polarization could be attributed to hydrogen-related dipoles. In addition, using low-frequency C-V characterization leads to clear detection of 100 ppm hydrogen even at room temperature where it is hard to detect hydrogen by using conventional current-voltage (I-V characterization, suggesting that low-frequency C-V method would be effective in detecting very low hydrogen concentrations.

  10. Determination of hydrogen in metals and alloys

    International Nuclear Information System (INIS)

    Sayi, Y.S.; Ramanjaneyulu, P.S.; Ramakumar, K.L.

    2008-01-01

    Hydrogen will be invariably present in all materials. Its presence in excess is harmful and sometimes calamitous. Hydrogen embrittlement can occur quite readily in most high strength materials, irrespective of their composition or structure. It is therefore essential to maintain low levels of hydrogen. To know the amount of hydrogen present in the materials, it is essential to determine it with high degree of precision and accuracy. It is required to give the uncertainty associated with the measurement to increase the confidence on measurements. Several methodologies are available for the determination of hydrogen. It its isotope, deuterium, also co-exists it becomes all the more difficult to determine these individually. Hot vacuum extraction cum quadrupole mass spectrometry (HVE-QMS) developed in our laboratory to determine hydrogen and deuterium is routinely employed for the determination of hydrogen and deuterium in metals and alloys. The present paper deals in detail about our experiences with HVE-QMS and estimation of uncertainty associated in this methodology. (author)

  11. Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

    Science.gov (United States)

    Milani, Barbara; Crottib, Corrado; Farnetti, Erica

    2008-09-14

    Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

  12. Rhodium-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Ketones: A General Approach to Chiral α-amino Ketones.

    Science.gov (United States)

    Gao, Wenchao; Wang, Qingli; Xie, Yun; Lv, Hui; Zhang, Xumu

    2016-01-01

    Rhodium/DuanPhos-catalyzed asymmetric hydrogenation of aliphatic α-dehydroamino ketones has been achieved and afforded chiral α-amino ketones in high yields and excellent enantioselectives (up to 99 % ee), which could be reduced further to chiral β-amino alcohols by LiAlH(tBuO)3 with good yields. This protocol provides a readily accessible route for the synthesis of chiral α-amino ketones and chiral β-amino alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Hydrogen axion star: metallic hydrogen bound to a QCD axion BEC

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Yang; Barger, Vernon; Berger, Joshua [Department of Physics, University of Wisconsin-Madison,1150 University Ave, Madison, WI 53706 (United States)

    2016-12-23

    As a cold dark matter candidate, the QCD axion may form Bose-Einstein condensates, called axion stars, with masses around 10{sup −11} M{sub ⊙}. In this paper, we point out that a brand new astrophysical object, a Hydrogen Axion Star (HAS), may well be formed by ordinary baryonic matter becoming gravitationally bound to an axion star. We study the properties of the HAS and find that the hydrogen cloud has a high pressure and temperature in the center and is likely in the liquid metallic hydrogen state. Because of the high particle number densities for both the axion star and the hydrogen cloud, the feeble interaction between axion and hydrogen can still generate enough internal power, around 10{sup 13} W×(m{sub a}/5 meV){sup 4}, to make these objects luminous point sources. High resolution ultraviolet, optical and infrared telescopes can discover HAS via black-body radiation.

  14. Metal-hydrogen systems with an exceptionally large and tunable thermodynamic destabilization

    NARCIS (Netherlands)

    Ngene, Peter; Longo, Alessandro; Mooij, L.P.A.; Bras, Wim; Dam, B.

    2017-01-01

    Hydrogen is a key element in the energy transition. Hydrogen-metal systems have been studied for various energy-related applications, e.g., for their use in reversible hydrogen storage, catalysis, hydrogen sensing, and rechargeable batteries. These applications depend strongly on the

  15. NATO International Symposium on the Electronic Structure and Properties of Hydrogen in Metals

    CERN Document Server

    Satterthwaite, C

    1983-01-01

    Hydrogen is the smallest impurity atom that can be implanted in a metallic host. Its small mass and strong interaction with the host electrons and nuclei are responsible for many anomalous and interesting solid state effects. In addition, hydrogen in metals gives rise to a number of technological problems such as hydrogen embrittlement, hydrogen storage, radiation hardening, first wall problems associated with nuclear fusion reactors, and degradation of the fuel cladding in fission reactors. Both the fundamental effects and applied problems have stimulated a great deal of inter­ est in the study of metal hydrogen systems in recent years. This is evident from a growing list of publications as well as several international conferences held in this field during the past decade. It is clear that a fundamental understanding of these problems re­ quires a firm knowledge of the basic interactions between hydrogen, host metal atoms, intrinsic lattice defects and electrons. This understanding is made particularly di...

  16. Metal-inorganic-organic matrices as efficient sorbents for hydrogen storage.

    Science.gov (United States)

    Azzouz, Abdelkrim; Nousir, Saadia; Bouazizi, Nabil; Roy, René

    2015-03-01

    Stabilization of metal nanoparticles (MNPs) without re-aggregation is a major challenge. An unprecedented strategy is developed for achieving high dispersion of copper(0) or palladium(0) on montmorillonite-supported diethanolamine or thioglycerol. This results in novel metal-inorganic-organic matrices (MIOM) that readily capture hydrogen at ambient conditions, with easy release under air stream. Hydrogen retention appears to involve mainly physical interactions, slightly stronger on thioglycerol-based MIOM (S-MIOM). Thermal enhancement of desorption suggests also a contribution of chemical interactions. The increase of hydrogen uptake with prolonged contact times arises from diffusion hindrance, which appears to be beneficial by favoring hydrogen entrapment. Even with compact structures, MIOMs act as efficient sorbents with much higher efficiency factor (1.14-1.17 mmol H 2 m(-2)) than many other sophisticated adsorbents reported in the literature. This opens new prospects for hydrogen storage and potential applications in microfluidic hydrogenation reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Transition metal-catalyzed carbocyclization of nitrogen and oxygen-tethered 1,n-enynes and diynes: synthesis of five or six-membered heterocyclic compounds.

    Science.gov (United States)

    Zhang, Di-Han; Zhang, Zhen; Shi, Min

    2012-10-25

    Cycloisomerization of 1,n-enynes and diynes is a powerful method in organic synthesis to access heterocyclic compounds and has drawn increasing attention from organic chemists. In this paper, we attempted to summarize our recent results on the transition metal-catalyzed cycloisomerization to synthesize five or six-membered heterocyclic compounds using 1,n-enynes and diynes having a propargylic ester moiety. First, we will describe the synthesis of 2,3-disubstituted 3-pyrrolines via gold catalyzed cycloisomerization of 1,6-diynes. In addition, we will also disclose a novel silver catalyzed tandem 1,3-acyloxy migration/Mannich-type addition/elimination of the sulfonyl group of N-sulfonylhydrazone-propargylic esters to 5,6-dihydropyridazin-4-one derivatives. Furthermore, we will introduce three interesting examples of the synthesis of bicyclic compounds via titanium or rhodium catalyzed carbocyclization of enynes. In this context, we have presented that 1,n-enynes and diynes containing propargylic esters are highly reactive and useful starting materials for the cycloisomerization catalyzed by a transition metal catalyst.

  18. Solubility of hydrogen in transition metals

    International Nuclear Information System (INIS)

    Lee, H.M.

    1976-01-01

    Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

  19. First-principles study of hydrogen diffusion in transition metal Rhodium

    International Nuclear Information System (INIS)

    Bao, Wulijibilige; Cui, Xin; Wang, Zhi-Ping

    2015-01-01

    In this study, the diffuse pattern and path of hydrogen in transition metal rhodium are investigated by the first-principles calculations. Density functional theory is used to calculate the system energies of hydrogen atom occupying different positions in rhodium crystal lattice. The results indicate that the most stable position of hydrogen atom in rhodium crystal lattice locates at the octahedral interstice, and the tetrahedral interstice is the second stable site. The activation barrier energy for the diffusion of atomic hydrogen in transition metal rhodium is quantified by determining the most favorable path, i.e., the minimum-energy pathway for diffusion, that is the indirect octahedral-tetrahedral-octahedral (O-T-O) pathway, and the activation energy is 0.8345eV

  20. Magnesium nanoparticles with transition metal decoration for hydrogen storage

    International Nuclear Information System (INIS)

    Pasquini, Luca; Callini, Elsa; Brighi, Matteo; Boscherini, Federico; Montone, Amelia; Jensen, Torben R.; Maurizio, Chiara; Vittori Antisari, Marco; Bonetti, Ennio

    2011-01-01

    We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.

  1. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

    Science.gov (United States)

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  2. Zero-Valent Metallic Treatment System and Its Application for Removal and Remediation of Polychlorinated Biphenyls (Pcbs)

    Science.gov (United States)

    Quinn, Jacqueline W. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor); Brooks, Kathleen B. (Inventor)

    2012-01-01

    PCBs are removed from contaminated media using a treatment system including zero-valent metal particles and an organic hydrogen donating solvent. The treatment system may include a weak acid in order to eliminate the need for a coating of catalytic noble metal on the zero-valent metal particles. If catalyzed zero-valent metal particles are used, the treatment system may include an organic hydrogen donating solvent that is a non-water solvent. The treatment system may be provided as a "paste-like" system that is preferably applied to natural media and ex-situ structures to eliminate PCBs.

  3. The metal-carbon-fluorine system for improving hydrogen storage by using metal and fluorine with different levels of electronegativity

    Energy Technology Data Exchange (ETDEWEB)

    Im, Ji Sun; Lee, Young-Seak [Department of Fine Chemical Engineering and Applied Chemistry, BK21-E2M, Chungnam National University, Daejeon 305-764 (Korea); Park, Soo-Jin [Department of Chemistry, Inha University, Incheon 402-751 (Korea)

    2009-02-15

    In order to improve the capacity of hydrogen storage using activated carbon nanofibers, metal and fluorine were introduced into the activated carbon nanofibers by electrospinning, heat treatment, and direct fluorination. The pore structure of the samples was developed by the KOH activation process and investigated using nitrogen isotherms and micropore size distribution. The specific surface area and total pore volume approached 2800 m{sup 2}/g and 2.7 cc/g, respectively. Because of the electronegativity gap between the two elements (metal and fluorine), the electron of a hydrogen molecule can be attracted to one side. This reaction effectively guides the hydrogen molecule into the carbon nanofibers. The amount of hydrogen storage was dramatically increased in this metal-carbon-fluorine system; hydrogen content was as high as 3.2 wt%. (author)

  4. Kinetics of catalyzed tritium oxidation in air at ambient temperature

    International Nuclear Information System (INIS)

    Sherwood, A.E.

    1980-01-01

    Tritium/air oxidation kinetic data are derived from measurements carried out with three catalysts. All experiments were carried out at room temperature - a regime that provides a severe test for catalyst effectiveness. Each catalyst consists of a high-surface-area substrate in pelletized form, onto which precious metal has been dispersed. The metal/substrate combinations investigated are: platinum/alumina, palladium/kaolin, and paladium/zeolite. Each of the dispersed-metal catalysts is extremely effective in promoting tritium oxidation in comparison with self-catalyzed atmospheric conversion; equivalent first-order rate constants are higher by roughly nine orders of magnitude. Electron-microprobe scans reveal that the dispersed metal is deposited near the outer surface of the catalyst, with metal concentration decreasing exponentially from the pellet surface. The platinum-based catalyst is more effective than the palladium catalysts on a surface-area basis by about a factor of three. Rate coefficients are determined from concentration decay following a spike injection of tritium into an air-filled enclosure processed by recirculation through an oxidation/adsorption system. The catalytic reaction is first-order in tritium concentration in the range 10 to 10 5 μCi/m 3 (4 ppt-40 ppB). Addition of hydrogen carrier gas is unnecessary. Catalytic activity for all three catalysts declines with time of exposure to air after activation, following a power-law decay with an exponent of -1/2. Reactivation with hot hydrogen gas effectively restores initial catalytic activity

  5. Effect of coexistent hydrogen isotopes on tracer diffusion of tritium in alpha phase of group-V metal-hydrogen systems

    International Nuclear Information System (INIS)

    Sakamoto, Kan; Hashizume, Kenichi; Sugisaki, Masayasu

    2009-01-01

    Tracer diffusion coefficients of tritium in the alpha phase of group-V metal-hydrogen systems, α-MH(D)xTy (M=V and Ta; x>>y), were measured in order to clarify the effects of coexistent hydrogen isotopes on the tritium diffusion behavior. The hydrogen concentration dependence of such behavior and the effects of the coexistent hydrogen isotopes (protium and deuterium) were determined. The results obtained in the present (for V and Ta) and previous (for Nb) studies revealed that tritium diffusion was definitely dependent on hydrogen concentration but was not so sensitive to the kind of coexistent hydrogen isotopes. By summarizing those data, it was found that the hydrogen concentration dependence of the tracer diffusion coefficient of tritium in the alpha phase of group-V metals could be roughly expressed by a single empirical curve. (author)

  6. The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

    Science.gov (United States)

    Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

    2014-11-28

    In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

  7. Development of composite metallic membranes for hydrogen purification

    International Nuclear Information System (INIS)

    Gaillard, F.

    2003-12-01

    Fuel cells are able to convert chemical energy into electric power. There are different types of cells; the best for automotive applications are Proton Exchange Membrane Fuel Cells. But, these systems need hydrogen of high purity. However, fuel reforming generates a mixture of gases, from which hydrogen has to be extracted before supplying the electrochemical cell. The best way for the purification of hydrogen is the membrane separation technology. Palladium is selectively permeable to hydrogen and this is the reason why this metal is largely used for the membrane development. This work deals with the development of hydrogen-selective membranes by deposition of a thin film of palladium onto a porous mechanical support. For this, we have used the electroless plating technique: a palladium salt and a reducing agent are mixed and the deposition takes place onto the catalytic surface of the substrate. After bibliographic investigations, experimental studies have been performed first with a dense metallic substrate in order to better understand the different parameters controlling the deposition. First of all, potentiometric measurements have been carried out to follow the electrochemical reactions in the bath. Then, kinetic measurements of the coating thickness have been recorded to understand the effect of the bath conditions on the yield and the adhesion of the film. Finally, the electroless plating method has been applied to deposit palladium membranes onto porous stainless steel substrates. After optimisation, the resulting membranes were tested for their hydrogen permeation properties. (author)

  8. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

    2018-03-06

    Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

  9. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction. Final technical report, September 1, 1988--December 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.

    1992-04-07

    The ultimate objective of this research has been to uncover novel reagents and experimental conditions for heteroatom removal and hydrogen transfer processes, which would be applicable to the liquefaction of coal under low-severity conditions. To this end, one phase of this research has investigated the cleavage of carbon-heteroatom bonds involving sulfur, oxygen, nitrogen and halogen by subvalent transition-metal complexes. A second phase of the study has assessed the capability of the same transition-metal complexes or of organoaluminum Lewis acids to catalyze the cleavage of carbon-hydrogen bonds in aromatics and hence to promote hydrogen shuttling. Finally, a third phase of our work has uncovered a remarkable synergistic effect of combinations of transition metals with organoaluminum Lewis acids on hydrogen shuttling between aromatics and hydroaromatics. (VC)

  11. Ultrapure hydrogen thermal compressor based on metal hydrides for fuel cells and hybrid vehicles

    International Nuclear Information System (INIS)

    Almasan, V.; Biris, A.; Coldea, I.; Lupu, D.; Misan, I.; Popeneciu, G.; Ardelean, O.

    2007-01-01

    Full text: In hydrogen economy, efficient compressors are indispensable elements in the storage, transport and distribution of the produced hydrogen. Energetic efficient technologies can contribute to H 2 pipelines transport to the point of use and to distribute H 2 by refuelling stations. Characteristic for metal hydrides systems is the wide area of possibilities to absorb hydrogen at low pressure from any source of hydrogen, to store and deliver it hydrogen at high pressure (compression ratio more than 30). On the basis of innovative concepts and advanced materials for H 2 storage/compression (and fast thermal transfer), a fast mass (H 2 ) and heat transfer unit will be developed suitable to be integrated in a 3 stage thermal compressor. Metal hydrides used for a three stage hydrogen compression system must have different equilibrium pressures, namely: for stage 1, low pressure H 2 absorption and resistant to poisoning with impurities of hydrogen, for stage 2, medium pressure H 2 absorption and for stage 3, high pressure hydrogen delivery (120 bar). In the case of compression device based on metallic hydrides the most important properties are the hydrogen absorption/desorption rate, a smaller process enthalpy and a great structural stability on long term hydrogen absorption/desorption cycling. These properties require metal hydrides with large differences between the hydrogen absorption and desorption pressures at equilibrium, within a rather small temperature range. The main goal of this work is to search and develop metal hydride integrated systems for hydrogen purification, storage and compression. After a careful screening three hydrogen absorbing alloys will be selected. After selection, the work up of the alloys composition on the bases of detailed solid state studies, new multi-component alloys will be developed, with suitable thermodynamic and kinetic properties for a hydrogen compressor. The results of the study are the following: new types of hydrogen

  12. Plasma-plasmonics synergy in the Ga-catalyzed growth of Si-nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Bianco, Giuseppe Valerio, E-mail: giuseppevalerio.bianco@cnr.it [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Giangregorio, Maria M.; Capezzuto, Pio [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Losurdo, Maria [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Department of Electrical and Computer Engineering, Duke University, Durham, NC 27708 (United States); Kim, Tong-Ho; Brown, April S. [Department of Electrical and Computer Engineering, Duke University, Durham, NC 27708 (United States); Bruno, Giovanni, E-mail: giovanni.bruno@ba.imip.cnr.it [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy)

    2012-06-05

    This paper reports on the growth of Si nanowires (NWs) by SiH{sub 4}/H{sub 2} plasmas using the non-noble Ga-nanoparticles (NPs) catalysts. A comparative investigation of conventional Si-NWs vapour-liquid-solid (VLS) growth catalyzed by Au NPs is also reported. We investigate the use of a hydrogen plasma and of a SiH{sub 4}/H{sub 2} plasma for removing Ga oxide shell and for enhancing the Si dissolution into the catalyst, respectively. By exploiting the Ga NPs surface plasmon resonance (SPR) sensitivity to their surface chemistry, the SPR characteristic of Ga NPs has been monitored by real time spectroscopic ellipsometry in order to control the hydrogen plasma/Ga NPs interaction and the involved processes (oxide removal and NPs dissolution by volatile gallium hydride). Using in situ laser reflectance interferometry the metal catalyzed Si NWs growth process has been investigated to find the effect of the plasma activation on the growth kinetics. The role of atomic hydrogen in the NWs growth mechanism and, in particular, in the SiH{sub 4} dissolution into the catalysts, is discussed. We show that while Au catalysts because of the re-aggregation of NPs yields NWs that do not correspond to the original size of the Au NPs catalyst, the NWs grown by the Ga catalyst retains the diameter dictated by the size of the Ga NPs. Therefore, the advantage of Ga NPs as catalysts for controlling NWs diameter is demonstrated.

  13. Heat of solution and site energies of hydrogen in disordered transition-metal alloys

    International Nuclear Information System (INIS)

    Brouwer, R.C.; Griessen, R.

    1989-01-01

    Site energies, long-range effective hydrogen-hydrogen interactions, and the enthalpy of solution in transition-metal alloys are calculated by means of an embedded-cluster model. The energy of a hydrogen atom is assumed to be predominantly determined by the first shell of neighboring metal atoms. The semiempirical local band-structure model is used to calculate the energy of the hydrogen atoms in the cluster, taking into account local deviations from the average lattice constant. The increase in the solubility limit and the weak dependence of the enthalpy of solution on hydrogen concentration in disordered alloys are discussed. Calculated site energies and enthalpies of solution in the alloys are compared with experimental data, and good agreement is found. Due to the strong interactions with the nearest-neighbor metal atoms, hydrogen atoms can be used to determine local lattice separations and the extent of short-range order in ''disordered'' alloys

  14. Hydrogen isotope exchange in metal hydride columns

    International Nuclear Information System (INIS)

    Wiswall, R.; Reilly, J.; Bloch, F.; Wirsing, E.

    1977-01-01

    Several metal hydrides were shown to act as chromatographic media for hydrogen isotopes. The procedure was to equilibrate a column of hydride with flowing hydrogen, inject a small quantity of tritium tracer, and observe its elution behavior. Characteristic retention times were found. From these and the extent of widening of the tritium band, the heights equivalent to a theoretical plate could be calculated. Values of around 1 cm were obtained. The following are the metals whose hydrides were studied, together with the temperature ranges in which chromatographic behavior was observed: vanadium, 0 to 70 0 C; zirconium, 500 to 600 0 C; LaNi 5 , -78 to +30 0 C; Mg 2 Ni, 300 to 375 0 C; palladium, 0 to 70 0 C. A dual-temperature isotope separation process based on hydride chromatography was demonstrated. In this, a column was caused to cycle between two temperatures while being supplied with a constant stream of tritium-traced hydrogen. Each half-cycle was continued until ''breakthrough,'' i.e., until the tritium concentration in the effluent was the same as that in the feed. Up to that point, the effluent was enriched or depleted in tritium, by up to 20%

  15. New vistas in the determination of hydrogen in aerospace engine metal alloys

    Science.gov (United States)

    Danford, M. D.

    1986-01-01

    The application of diffusion theory to the analysis of hydrogen desorption data has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, were studied in this work. For the nickel base alloys, it was found that the hydrogen distributions after electrolytic charging conformed closely to those which would be predicted by diffusion theory. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, were essentially uniform in nature, which would not be predicted by diffusion theory. Finally, it has been found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the 'fast' hydrogen is not due to surface and subsurface hydride formation, as was originally proposed.

  16. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    International Nuclear Information System (INIS)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

    2017-01-01

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

  17. Hydrogen isotope exchange of organic compounds in dilute acid at elevated temperatures

    International Nuclear Information System (INIS)

    Werstiuk, N.H.

    1987-01-01

    Introduction of one or more deuterium (or tritium) atoms into organic molecules can be accomplished in many ways depending on the nature of the substrate and the extent and sterochemistry of deuteriation or tritiation required. Some of the common methods include acid- and base-catalyzed exchange of carbonyl compounds, metal hydride reductions, dissolving metal reductions, catalytic reduction of double bonds, chromatographic exchange, homogeneous and heterogeneous metal-catalyzed exchange, base-catalyzed exchange of carbon acids other than carbonyl compounds and acid-catalyzed exchange via electrophilic substitution. Only the latter three methods have been used for perdeuteriation of organic compounds. A very useful compendium of labeling methods with examples has been available to chemists for some time. Although metal-catalyzed exchange has been used extensively, the method suffers from some deficiencies: irreproducibility of catalyst surfaces, catalyst poisoning, side reactions such as coupling and hydrogenolysis of labile groups and low deuterium incorporation. Usually a number of cycles are required with fresh catalyst and fresh deuterium source to achieve substantial isotope incorporation. Acid-catalyzed exchange of aromatics and alkenes, strongly acidic media such as liquid DBr, concentrated DBr, acetic acid/stannic chloride, concentrated D 3 PO 4 , concentrated DC1, D 3 PO 4 /BF 3 SO 2 , 50-80% D 2 SO 4 and DFSO 4 /SbF 5 at moderate temperatures (<100 degrees) have been used to effect exchange. The methods are not particularly suitable for large scale deuteriations because of the cost and the fact that the recovery and upgrading of the diluted deuterium pool is difficult. This paper describes the hydrogen isotope exchange of a variety of organic compounds in dilute aqueous acid (0.1-0.5 M) at elevated temperatures (150-300 degrees)

  18. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  19. Transition metal-catalyzed couplings of alkynes to 1,3-enynes: modern methods and synthetic applications.

    Science.gov (United States)

    Trost, Barry M; Masters, James T

    2016-04-21

    The metal-catalyzed coupling of alkynes is a powerful method for the preparation of 1,3-enynes, compounds that are of broad interest in organic synthesis. Numerous strategies have been developed for the homo- and cross coupling of alkynes to enynes via transition metal catalysis. In such reactions, a major issue is the control of regio-, stereo-, and, where applicable, chemoselectivity. Herein, we highlight prominent methods for the selective synthesis of these valuable compounds. Further, we illustrate the utility of these processes through specific examples of their application in carbocycle, heterocycle, and natural product syntheses.

  20. A Biomimetic Approach to New Adsorptive Hydrogen Storage Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Hongcai J [Texas A& M University

    2015-08-12

    In the past decades, there has been an escalation of interest in the study of MOFs due to their fascinating structures and intriguing application potentials. Their exceptionally high surface areas, uniform yet tunable pore sizes, and well-defined adsorbate-MOF interaction sites make them suitable for hydrogen storage. Various strategies to increase the hydrogen capacity of MOFs, such as constructing pore sizes comparable to hydrogen molecules, increasing surface area and pore volume, utilizing catenation, and introducing coordinatively unsaturated metal centers (UMCs) have been widely explored to increase the hydrogen uptake of the MOFs. MOFs with hydrogen uptake approaching the DOE gravimetric storage goal under reasonable pressure but cryo- temperature (typically 77 K) were achieved. However, the weak interaction between hydrogen molecules and MOFs has been the major hurdle limiting the hydrogen uptake of MOFs at ambient temperature. Along the road, we have realized both high surface area and strong interaction between framework and hydrogen are equally essential for porous materials to be practically applicable in Hydrogen storage. Increasing the isosteric heats of adsorption for hydrogen through the introduction of active centers into the framework could have great potential on rendering the framework with strong interaction toward hydrogen. Approaches on increasing the surface areas and improving hydrogen affinity by optimizing size and structure of the pores and the alignment of active centers around the pores in frameworks have been pursued, for example: (a) the introduction of coordinatively UMC (represents a metal center missing multiple ligands) with potential capability of multiple dihydrogen-binding (Kubas type, non-dissociative) per UMC, (b) the design and synthesis of proton-rich MOFs in which a + H3 binds dihydrogen just like a metal ion does, and (c) the preparation of MOFs and PPNs with well aligned internal electric fields. We believe the

  1. Complex Metal Hydrides for hydrogen storage and solid-state ion conductors

    DEFF Research Database (Denmark)

    Payandeh GharibDoust, SeyedHosein

    and electricity in batteries. However, both hydrogen and electricity must be stored in a very dense way to be useful, e.g. for mobile applications. Complex metal hydrides have high hydrogen density and have been studied during the past twenty years in hydrogen storage systems. Moreover, they have shown high ionic...... conductivities which promote their application as solid electrolytes in batteries. This dissertation presents the synthesis and characterization of a variety of complex metal hydrides and explores their hydrogen storage properties and ionic conductivity. Five halide free rare earth borohydrides RE(BH4)3, (RE...... = La, Ce, Pr, Nd, Er) have been synthesized, which pave the way for studying the polymorphic transition in these compounds, obtaining new bimetallic borohydrides and designing new reactive hydride composites with improved hydrogen storage capacities. Two novel polymorphs of Pr(BH4)3 are identified...

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

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-06-25

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

  3. Investigation of transition metal-catalyzed nitrene transfer reactions in water.

    Science.gov (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

    2018-04-11

    Transition metal-catalyzed nitrene transfer is a powerful method for incorporating new CN bonds into relatively unfunctionalized scaffolds. In this communication, we report the first examples of site- and chemoselective CH bond amination reactions in aqueous media. The unexpected ability to employ water as the solvent in these reactions is advantageous in that it eliminates toxic solvent use and enables reactions to be run at increased concentrations with lower oxidant loadings. Using water as the reaction medium has potential to expand the scope of nitrene transfer to encompass a variety of biomolecules and highly polar substrates, as well as enable pH control over the site-selectivity of CH bond amination. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Recyclable hydrogen storage system composed of ammonia and alkali metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Hikaru [Department of Quantum Matter, AdSM, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Miyaoka, Hiroki; Hino, Satoshi [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Nakanishi, Haruyuki [Higashi-Fuji Technical Center, Toyota Motor Corporation, 1200 Misyuku, Susono, Shizuoka 410-1193 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Department of Quantum Matter, AdSM, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan)

    2009-12-15

    Ammonia (NH{sub 3}) reacts with alkali metal hydrides MH (M = Li, Na, and K) in an exothermic reaction to release hydrogen (H{sub 2}) at room temperature, resulting that alkali metal amides (MNH{sub 2}) which are formed as by-products. In this work, hydrogen desorption properties of these systems and the condition for the recycle from MNH{sub 2} back to MH were investigated systematically. For the hydrogen desorption reaction, the reactivities of MH with NH{sub 3} were better following the atomic number of M on the periodic table, Li < Na < K. It was confirmed that the hydrogen absorption reaction of all the systems proceeded under 0.5 MPa of H{sub 2} flow condition below 300 C. (author)

  5. Microstructural Effects on Hydrogen Delayed Fracture of 600 MPa and 800 MPa grade Deposited Weld Metal

    International Nuclear Information System (INIS)

    Kang, Hee Jae; Lee, Tae Woo; Cho, Kyung Mox; Kang, Namhyun; Yoon, Byung Hyun; Park, Seo Jeong; Chang, Woong Seong

    2012-01-01

    Hydrogen-delayed fracture (HDF) was analyzed from the deposited weld metals of 600-MPa and 800-MPa flux-cored arc (FCA) welding wires, and then from the diffusible hydrogen behavior of the weld zone. Two types of deposited weld metal, that is, rutile weld metal and alkali weld metal, were used for each strength level. Constant loading test (CLT) and thermal desorption spectrometry (TDS) analysis were conducted on the hydrogen pre-charged specimens electrochemically for 72 h. The effects of microstructures such as acicular ferrite, grain-boundary ferrite, and low-temperature-transformation phase on the time-to failure and amount of diffusible hydrogen were analyzed. The fracture time for hydrogen-purged specimens in the constant loading tests decreased as the grain size of acicular ferrite decreased. The major trapping site for diffusible hydrogen was the grain boundary, as determined by calculating the activation energies for hydrogen detrapping. As the strength was increased and alkali weld metal was used, the resistance to HDF decreased.

  6. Hydrogen permeation resistant layers for liquid metal reactors

    International Nuclear Information System (INIS)

    McGuire, J.C.

    1980-03-01

    Reviewing the literature in the tritium diffusion field one can readily see a wide divergence in results for both the response of permeation rate to pressure, and the effect of oxide layers on total permeation rates. The basic mechanism of protective oxide layers is discussed. Two coatings which are less hydrogen permeable than the best naturally occurring oxide are described. The work described is part of an HEDL-ANL cooperative research program on Tritium Permeation in Liquid Metal Cooled Reactors. This includes permeation work on hydrogen, deuterium, and tritium with the hydrogen-deuterium research leading to the developments presented

  7. Hydrogen formation in metals and alloys during fusion reactor operation

    International Nuclear Information System (INIS)

    Zimin, S.; Takatsu, Hideyuki; Mori, Seiji

    1994-08-01

    The results of neutron transport calculations of the hydrogen formation based on the JENDL gas-production cross section file are discussed for some metals and alloys, namely 51 V, Cr, Fe, Ni, Mo, austenitic stainless steel (Ti modified 316SS:PCA), ferritic steel (Fe-8Cr-2W:F82H) and the vanadium-base alloy (V-5Cr-5Ti). Impact of the steel fraction in steel/water homogeneous blanket/shield compositions on the hydrogen formation rate in above-mentioned metals and alloys is discussed both for the hydrogen formation in the first wall and the blanket/shield components. The results obtained for the first wall are compared with those for the helium formation obtained at JAERI by the same calculational conditions. Hydrogen formation rates at the first wall having 51 V, Cr, Fe, Ni and Mo are larger than those of helium by 3-8 times. (author)

  8. 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). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2005-01-01

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

  10. Nuclear processes in deuterium/natural hydrogen-metal systems

    International Nuclear Information System (INIS)

    Zelensky, V.F.

    2013-01-01

    The survey presents the analysis of the phenomena taking place in deuterium - metal and natural hydrogen - metal systems under cold fusion experimental conditions. The cold fusion experiments have shown that the generation of heat and helium in the deuterium-metal system without emission of energetic gamma-quanta is the result of occurrence of a chain of chemical, physical and nuclear processes observed in the system, culminating in both the fusion of deuterium nuclei and the formation of a virtual, electron-modified excited 4He nucleus. The excitation energy of the helium nucleus is transferred to the matrix through emission of conversion electrons, and that, under appropriate conditions, provides a persistent synthesis of deuterium. The processes occurring in the deuterium/natural hydrogen - metal systems have come to be known as chemonuclear DD- and HD-fusion. The mechanism of stimulation of weak interaction reactions under chemonuclear deuterium fusion conditions by means of strong interaction reactions has been proposed. The results of numerous experiments discussed in the survey bear witness to the validity of chemonuclear fusion. From the facts discussed it is concluded that the chemonuclear deuterium fusion scenario as presented in this paper may serve as a basis for expansion of deeper research and development of this ecologically clean energy source. It is shown that the natural hydrogen-based system, containing 0.015% of deuterium, also has good prospects as an energy source. The chemonuclear fusion processes do not require going beyond the scope of traditional physics for their explanation

  11. Catalytic activation of molecular hydrogen in alkyne hydrogenation reactions by lanthanide metal vapor reaction products

    International Nuclear Information System (INIS)

    Evans, W.J.; Bloom, I.; Engerer, S.C.

    1983-01-01

    A rotary metal vapor was used in the synthesis of Lu, Er, Nd, Sm, Yb, and La alkyne, diene, and phosphine complexes. A typical catalytic hydrogenation experiment is described. The lanthanide metal vapor product is dissolved in tetrahydrofuran or toluene and placed in a pressure reaction vessel 3-hexyne (or another substrate) is added, the chamber attached to a high vacuum line, cooled to -196 0 C, evacuated, warmed to ambient temperature and hydrogen is added. The solution is stirred magnetically while the pressure in monitored. The reaction products were analyzed by gas chromatography. Rates and products of various systems are listed. This preliminary survey indicates that catalytic reaction chemistry is available to these metals in a wide range of coordination environments. Attempts to characterize these compounds are hampered by their paramagnetic nature and their tendency to polymerize

  12. Impact of different metal turbidities on radiolytic hydrogen generation in nuclear power plants

    International Nuclear Information System (INIS)

    Kumbhar, A.G.; Belapurkar, A.D.; Venkateswaran, G.; Kishore, K.

    2005-01-01

    Radiolytic hydrogen generation on γ irradiation of turbid solutions containing metal turbidities such as titanium, nickel, iron, chromium, copper, indium, and aluminium was studied. It is suggested that the chemical reactivity of the metal in the turbid solution with e aq -/H/OH produced by radiolysis of water interferes with the recombination reactions which destroy H 2 and H 2 O 2 , thus leading to higher yield of hydrogen. The rate of generation of hydrogen and the G(H 2 ) value is related to the reactivity of the metal ion/hydroxylated species with the free radicals. (orig.)

  13. Aerobic Transition-Metal-Free Synthesis of 2,3-Diarylindoles and 5-Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jin; Moon, Hye Ran; Kim, Su Yeon; Kim, Jae Nyoung [Chonnam National Un iversity, Gwangju (Korea, Republic of)

    2016-01-15

    2,3-diarylindoles and 5-aryluracils were synthesized by ONSH pathway under transition-metal-free conditions in good to moderate yields using molecular oxygen as an oxidant. As 2,3-diarylindoles have been found in many biologically important compounds, the synthesis of this scaffold has received much attention. Most frequently, 2,3-diarylindoles have been prepared via palladium-catalyzed arylations of 2-arylindole with bromoarenes. During our recent transition metal-catalyzed arylations of indoles and uracils, we were interested in the arylation in the absence of an expensive transition metal catalyst.

  14. Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

    Science.gov (United States)

    Cao, Hujun; Richter, Theresia M M; Pistidda, Claudio; Chaudhary, Anna-Lisa; Santoru, Antonio; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Application of hydrogen isotopes and metal hydrides in future energy source

    Energy Technology Data Exchange (ETDEWEB)

    Guoqiang, Jiang [Sichuan Inst. of Materials and Technology, Chengdu, SC (China)

    1994-12-01

    The probable application of hydrogen isotopes and metal hydrides to future energy source is reviewed. Starting from existing state of China`s energy source, the importance for developing hydrogen energy and fusion energy is explained. It is suggested that the application investigation of hydrogen energy and hydrogen storage materials should be spurred and encouraged; keeping track of the development on tritium technology for fusion reactor is stressed.

  16. Application of hydrogen isotopes and metal hydrides in future energy source

    International Nuclear Information System (INIS)

    Jiang Guoqiang

    1994-12-01

    The probable application of hydrogen isotopes and metal hydrides to future energy source is reviewed. Starting from existing state of China's energy source, the importance for developing hydrogen energy and fusion energy is explained. It is suggested that the application investigation of hydrogen energy and hydrogen storage materials should be spurred and encouraged; keeping track of the development on tritium technology for fusion reactor is stressed

  17. γ-Sultam-cored N,N-ligands in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation of aryl ketones.

    Science.gov (United States)

    Rast, Slavko; Modec, Barbara; Stephan, Michel; Mohar, Barbara

    2016-02-14

    The synthesis of new enantiopure syn- and anti-3-(α-aminobenzyl)-benzo-γ-sultam ligands 6 and their application in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation (ATH) of ketones using formic acid/triethylamine is described. In particular, benzo-fused cyclic ketones afforded excellent enantioselectivities in reasonable time employing a low loading of the syn ligand-containing catalyst. A never-before-seen dynamic kinetic resolution (DKR) during reduction of a γ-keto carboxylic ester (S7) derivative of 1-indanone is realized leading as well to excellent induction.

  18. Transition metal-catalyzed carboxylation reactions with carbon dioxide.

    Science.gov (United States)

    Martin, Ruben; Tortajada, Andreu; Juliá-Hernández, Francisco; Borjesson, Marino; Moragas, Toni

    2018-05-03

    Driven by the inherent synthetic potential of CO2 as an abundant, inexpensive and renewable C1 chemical feedstock, the recent years have witnessed renewed interest in devising catalytic CO2 fixations into organic matter. Although the formation of C-C bonds via catalytic CO2 fixation remained rather limited for a long period of time, a close look into the recent literature data indicates that catalytic carboxylation reactions have entered a new era of exponential growth, evolving into a mature discipline that allows for streamlining the synthesis of carboxylic acids, building blocks of utmost relevance in industrial endeavours. These strategies have generally proven broadly applicability and convenient to perform. However, substantial challenges still need to be addressed reinforcing the need to cover metal-catalyzed carboxylation arena in a conceptual and concise manner, delineating the underlying new principles that are slowly emerging in this vibrant area of expertise. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Hydrogen adsorption in metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Senkovska, Irena; Kaskel, Stefan [Department of Inorganic Chemistry, Technical University, Dresden (Germany)

    2008-07-01

    Metal-Organic Frameworks (MOFs) have recently received considerable attention because of their high specific micropore volume and the ability to store gas molecules exceeding the storage capacity of traditional adsorbents. A variety of differences in the MOFs structures makes it difficult to analyze the influence of different factors on hydrogen uptake capabilities in MOFs. We have investigated the influence of the minor structural changes of the MOFs on their hydrogen storage capacity. The influence of the incorporated metal was shown for following isostructural compounds: Cu{sub 3}(BTC){sub 2} (BTC=1,3,5-benzenetricarboxylate) and Mo{sub 3}(BTC){sub 2}; Zn{sub 2}(BDC){sub 2}DABCO and Co{sub 2}(BDC){sub 2}DABCO (BDC=1,4-benzenedicarboxylate, DABCO=1,4-diazabicyclo[2.2.2]octane). Our research interest is directed also towards the discovery of new MOFs, as well as adjusting the pore dimensions of MOFs, using different building blocks, solvent and solvent mixtures, in order to improve gas uptake and adsorption properties. Magnesium-based MOFs were found with the same network topology, very small pore size and selective adsorption behaviour. They show a guest-induced reversible structure transformation due to the flexibility of the Mg{sub 3}-cluster and the organic linkers. This effect could be used for fitting the pore sizes and for the increase of gas sorption capability in Mg contained MOFs after all. The hydrogen adsorption was also studied in several Al-based IRMOFs.

  20. High capacity hydrogen absorption in transition-metal ethylene complexes: consequences of nanoclustering

    International Nuclear Information System (INIS)

    Phillips, A B; Shivaram, B S

    2009-01-01

    We have recently shown that organo-metallic complexes formed by laser ablating transition metals in ethylene are high hydrogen absorbers at room temperature (Phillips and Shivaram 2008 Phys. Rev. Lett. 100 105505). Here we show that the absorption percentage depends strongly on the ethylene pressure. High ethylene pressures (>100 mTorr) result in a lowered hydrogen uptake. Transmission electron microscopy measurements reveal that while low pressure ablations result in metal atoms dispersed uniformly on a near atomic scale, high pressure ones yield distinct nanoparticles with electron energy-loss spectroscopy demonstrating that the metal atoms are confined solely to the nanoparticles.

  1. Hydrogen-induced metallicity and strengthening of MoS{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Yakovkin, I.N., E-mail: yakov@iop.kiev.ua; Petrova, N.V.

    2014-04-15

    Highlights: • Hydrogen inserted into MoS{sub 2} bilayers increases the interlayer interaction. • Adsorbed or intercalated H monolayer makes the surface metallic. • Fermi surface of the H/MoS{sub 2} shows a significant nesting. - Abstract: The performed DFT calculations for MoS{sub 2} layers with adsorbed and intercalated hydrogen indicate that the atomic hydrogen monolayer makes the surface metallic. The physisorbed H{sub 2} does not affect electronic properties of the MoS{sub 2} monolayer, which remains a direct gap semiconductor. Due to forming S–H–S bonds, hydrogen atoms, intercalated into the space between MoS{sub 2} layers, increase the interlayer interaction from 0.12 eV to 0.60 eV. The related increase of the stiffness of the Mo–H–Mo layered system is of a primary importance for the interpretation of images of the surface obtained with the Ultrasonic Force Microscopy (Kolosov and Yamanaka, 1993) [42].

  2. Hydrogen storage in metallic hydrides: the hydrides of magnesium-nickel alloys

    International Nuclear Information System (INIS)

    Silva, E.P. da.

    1981-01-01

    The massive and common use of hydrogen as an energy carrier requires an adequate solution to the problem of storing it. High pressure or low temperatures are not entirely satisfactory, having each a limited range of applications. Reversible metal hydrides cover a range of applications intermediate to high pressure gas and low temperature liquid hydrogen, retaining very favorable safety and energy density characteristics, both for mobile and stationary applications. This work demonstrates the technical viability of storing hydrogen in metal hydrides of magnesium-nickel alloys. Also, it shows that technology, a product of science, can be generated within an academic environment, of the goal is clear, the demand outstanding and the means available. We review briefly theoretical models relating to metal hydride properties, specially the thermodynamics properties relevant to this work. We report our experimental results on hydrides of magnesium-nickel alloys of various compositions including data on structure, hydrogen storage capacities, reaction kinetics, pressure-composition isotherms. We selected a promising alloy for mass production, built and tested a modular storage tank based on the hydrides of the alloy, with a capacity for storing 10 Nm sup(3) of hydrogen of 1 atm and 20 sup(0)C. The tank weighs 46,3 Kg and has a volume of 21 l. (author)

  3. Hydrogen Doping into MoO3 Supports toward Modulated Metal-Support Interactions and Efficient Furfural Hydrogenation on Iridium Nanocatalysts.

    Science.gov (United States)

    Xie, Lifang; Chen, Ting; Chan, Hang Cheong; Shu, Yijin; Gao, Qingsheng

    2018-03-16

    As promising supports, reducible metal oxides afford strong metal-support interactions to achieve efficient catalysis, which relies on their band states and surface stoichiometry. In this study, in situ and controlled hydrogen doping (H doping) by means of H 2 spillover was employed to engineer the metal-support interactions in hydrogenated MoO x -supported Ir (Ir/H-MoO x ) catalysts and thus promote furfural hydrogenation to furfuryl alcohol. By easily varying the reduction temperature, the resulting H doping in a controlled manner tailors low-valence Mo species (Mo 5+ and Mo 4+ ) on H-MoO x supports, thereby promoting charge redistribution on Ir and H-MoO x interfaces. This further leads to clear differences in H 2 chemisorption on Ir, which illustrates its potential for catalytic hydrogenation. As expected, the optimal Ir/H-MoO x with controlled H doping afforded high activity (turnover frequency: 4.62 min -1 ) and selectivity (>99 %) in furfural hydrogenation under mild conditions (T=30 °C, PH2 =2 MPa), which means it performs among the best of current catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Characterisation of hydrocarbonaceous overlayers important in metal-catalysed selective hydrogenation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lennon, David; Warringham, Robbie [School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ (United Kingdom); Guidi, Tatiana [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX (United Kingdom); Parker, Stewart F., E-mail: stewart.parker@stfc.ac.uk [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX (United Kingdom)

    2013-12-12

    Highlights: • Inelastic neutron scattering spectroscopy of a commercial dehydrogenation catalyst. • The overlayer present on the catalyst is predominantly aliphatic. • A population of strongly hydrogen bonded hydroxyls is also present. - Abstract: The hydrogenation of alkynes to alkenes over supported metal catalysts is an important industrial process and it has been shown that hydrocarbonaceous overlayers are important in controlling selectivity profiles of metal-catalysed hydrogenation reactions. As a model system, we have selected propyne hydrogenation over a commercial Pd(5%)/Al{sub 2}O{sub 3} catalyst. Inelastic neutron scattering studies show that the C–H stretching mode ranges from 2850 to 3063 cm{sup −1}, indicating the mostly aliphatic nature of the overlayer and this is supported by the quantification of the carbon and hydrogen on the surface. There is also a population of strongly hydrogen-bonded hydroxyls, their presence would indicate that the overlayer probably contains some oxygen functionality. There is little evidence for any olefinic or aromatic species. This is distinctly different from the hydrogen-poor overlayers that are deposited on Ni/Al{sub 2}O{sub 3} catalysts during methane reforming.

  5. Predicted energy densitites for nickel-hydrogen and silver-hydrogen cells embodying metallic hydrides for hydrogen storage

    Science.gov (United States)

    Easter, R. W.

    1974-01-01

    Simplified design concepts were used to estimate gravimetric and volumetric energy densities for metal hydrogen battery cells for assessing the characteristics of cells containing metal hydrides as compared to gaseous storage cells, and for comparing nickel cathode and silver cathode systems. The silver cathode was found to yield superior energy densities in all cases considered. The inclusion of hydride forming materials yields cells with very high volumetric energy densities that also retain gravimetric energy densities nearly as high as those of gaseous storage cells.

  6. Quantum-mechanical approach to the state of hydrogen in b. c. c. metals

    Energy Technology Data Exchange (ETDEWEB)

    Fukai, Y; Sugimoto, H

    1980-01-01

    A first step towards consistent understanding of various properties of interstitial hydrogen in b.c.c. metals has been made by solving a Schroedinger equation for hydrogen atoms in the field of interaction with surrounding metal atoms. Properties investigated include the nature of self-trapped states, the relative stability of self-trapped configurations, the average stress field (P-tensor), the excitation energy to be determined by neutron spectroscopy, etc. Calculations were performed on hydrogen isotopes (H, D, T) in group-V metals (V, Nb, Ta), and good agreement was obtained with many different kinds of observations. Some predictions and tentative explanations are also presented.

  7. Quantum-mechanical approach to the state of hydrogen in B. C. C. metals

    Energy Technology Data Exchange (ETDEWEB)

    Fukai, Y; Sugimoto, H [Chuo Univ., Tokyo (Japan). Dept. of Physics

    1980-01-01

    A first step towards consistent understanding of various properties of interstitial hydrogen in B.C.C. metals has been made by solving a Schroedinger equation for hydrogen atoms in the field of interaction with surrounding metal atoms. Properties investigated include a nature of self-trapped states, a relative stability of self-trapped configurations, the average stress field (P-tensor), the excitation energy to be determined by neutron spectroscopy, etc. Calculations were performed on hydrogen isotopes (H, D, T) in group-V metals (V, Nb, Ta), and good agreement was obtained with many different kinds of observations. Some predictions and tentative explanations are also presented.

  8. Selective gettering of hydrogen in high pressure metal iodide lamps

    International Nuclear Information System (INIS)

    Kuus, G.

    1976-01-01

    One of the main problems in the manufacture of high pressure gas discharge lamps is the elimination of gaseous impurities from their arc tubes. Long degassing processes of all the lamp components are necessary in order to produce lamps with a low ignition voltage and good maintenance of the radiation properties. The investigation described deals with a selective getter place in the arc tube which can replace the long degassing process. The getter consists of a piece of yttrium encapsulated in thin tantalum foil. By this way it is possible to use the gettering action of tantalum and yttrium without having reaction between the metal iodide of the arc tube and yttrium. Yttrium is used because this metal can adsorb a large quantity of hydrogen even at a temperature of 1000 0 C. Hydrogen forms the main gaseous impurity in the high pressure metal iodide lamp. For this reason the adsorption properties like adsorption rate and capacity of the tantalum--yttrium getter for hydrogen are examined, and the results obtained from lamp experiments are given

  9. Metal-polypyridyl catalysts for electro- and photochemical reduction of water to hydrogen.

    Science.gov (United States)

    Zee, David Z; Chantarojsiri, Teera; Long, Jeffrey R; Chang, Christopher J

    2015-07-21

    Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an

  10. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com [Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung Jalan Ganeca 10 Gd. T.P. Rachmat, Bandung 40132 (Indonesia); Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id; Dipojono, H. K., E-mail: dipojono@tf.itb.ac.id

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  11. Optical hydrogen sensors based on metal-hydrides

    Science.gov (United States)

    Slaman, M.; Westerwaal, R.; Schreuders, H.; Dam, B.

    2012-06-01

    For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.

  12. Hydrogen generation from formic acid catalyzed by a metal complex under amine-free and aqueous conditions

    KAUST Repository

    Huang, Kuo-Wei

    2018-01-04

    The present invention provides a class of catalyst compounds that can safely and effectively release hydrogen gas from a chemical substrate without producing either noxious byproducts or byproducts that will deactivate the catalyst. The present invention provides catalysts used to produce hydrogen that has a satisfactory and sufficient lifespan (measured by turnover number (TON)), that has stability in the presence of moisture, air, acid, or impurities, promote a rapid reaction rate, and remain stable under the reaction conditions required for an effective hydrogen production system. Described herein are compounds for use as catalysts, as well as methods for producing hydrogen from formic acid and/or a formate using the disclosed catalysts. The methods include contacting formic acid and/or a formate with a catalyst as described herein, as well as methods of producing formic acid and/or a formate using the disclosed catalyst and methods for generating electricity using the catalysts described herein.

  13. Diatomite-supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts for selective hydrogenation of long-chain aliphatic esters.

    Science.gov (United States)

    Huang, Changliang; Zhang, Hongye; Zhao, Yanfei; Chen, Sha; Liu, Zhimin

    2012-11-15

    Diatomite supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts with various metal compositions were prepared and characterized by means of X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was demonstrated that the metal nanoparticles were uniformly distributed on the support, and their size was centered around 8 nm with a relatively narrow size distribution. The catalysts were used to catalyze hydrogenation of long-chain aliphatic esters, including methyl palmitate, methyl stearate, and methyl laurate. It was indicated that the all diatomite-supported Pd-based bimetal catalysts were active to the selective hydrogenation of long-chain esters to corresponding alcohols at 270°C, originated from the synergistic effect between the metal particles and the diatomite support. For the selective hydrogenation of methyl palmitate, Pd-Cu/diatomite with metal loading of 1% and Pd/Cu=3 displayed the highest performance, giving a 1-hexadecanol yield of 82.9% at the substrate conversion of 98.8%. Copyright © 2012 Elsevier Inc. All rights reserved.

  14. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Science.gov (United States)

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. The kinetic and mechanical aspects of hydrogen-induced failure in metals. Ph.D. Thesis, 1971

    Science.gov (United States)

    Nelson, H. G.

    1972-01-01

    Premature hydrogen-induced failure observed to occur in many metal systems involves three stages of fracture: (1) crack initiation, (2) stable slow crack growth, and (3) unstable rapid crack growth. The presence of hydrogen at some critical location on the metal surface or within the metal lattice was shown to influence one or both of the first two stages of brittle fracture but has a negligible effect on the unstable rapid crack growth stage. The relative influence of the applied parameters of time, temperature, etc., on the propensity of a metal to exhibit hydrogen induced premature failure was investigated.

  16. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

    Science.gov (United States)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

    2018-01-10

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Metal oxide-hydrogen secondary battery; Kinzoku sankabutsu-suiso niji denchi

    Energy Technology Data Exchange (ETDEWEB)

    Hosobuchi, H.; Edoi, M.; Katsumata, T.

    1995-06-06

    Recently, the metal oxide - hydrogen secondary battery characterized by employing the hydrogen storage alloy as the hydrogen negative electrode draws attention. However, the secondary batteries equipped with the negative electrode composed of hydrogen storage alloy powder have such shortcoming that the charge-discharge cycle life is rather short and it changes widely from battery to battery, as the hydrogen storage alloy is disintegrated. This invention solves the problem. Employing the alloy having a composition expressed as LmNi(w)Co(X)Mn(y)Al(z) (Lm = rare earth elements including La) can suppress the disintegration of hydrogen storage alloy powder during the charge-discharge cycle. In addition, controlling the oxygen content in the hydrogen storage alloy powder to 500 - 1500ppm can reduce the oxidation corrosion of the hydrogen storage alloy, resulting in suppression of its deterioration. 1 fig., 2 tabs.

  18. Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

    Science.gov (United States)

    Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

    2016-03-01

    Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

  19. Synthesis of Polycyclic Ring Systems Using Transition Metal Catalyzed Cyclizations of Diazo Alkynyl Ketones

    Directory of Open Access Journals (Sweden)

    Albert Padwa

    2000-12-01

    Full Text Available The rhodium(II-catalyzed reaction of α-diazo ketones bearing tethered alkyne units represents a new and useful method for the construction of a variety of substituted cyclopentenones. The process proceeds by addition of the rhodium-stabilized carbenoid onto the acetylenic π-bond to give a vinyl carbenoid intermediate. The resulting rhodium complex undergoes a wide assortment of reactions including cyclopropanation, 1,2-hydrogen migration, CH-insertion, addition to tethered alkynes and ylide formation. When 2-alkynyl-2-diazo-3-oxobutanoates were treated with a Rh(II-catalyst, furo[3,4-c]furans were formed in excellent yield.

  20. Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sagert, N H; Shaw-Wood, P E; Pouteau, R M.L. [Atomic Energy of Canada Ltd., Pinawa, Manitoba. Whiteshell Nuclear Research Establishment

    1975-11-01

    Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20% of various metal oxides. The oxides used were Cr/sub 2/O/sub 3/, MoO/sub 2/, MnO, WO/sub 2/-WO/sub 3/, and UO/sub 2/. Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide.

  1. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

    Science.gov (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

    2018-03-01

    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Theoretical examination of the trapping of ion-implanted hydrogen in metals

    International Nuclear Information System (INIS)

    Myers, S.M.; Nordlander, P.; Besenbacher, F.; Norskov, J.K.

    1986-01-01

    Theoretical analysis of the defect trapping of ion-implanted hydrogen in metals has been extended in two respects. A new transport formalism has been developed which takes account not only of the diffusion, trapping, and surface release of the hydrogen, which were included in earlier treatments, but also the diffusion, recombination, agglomeration, and surface annihilation of the vacancy and interstitial traps. In addition, effective-medium theory has been used to examine multiple hydrogen occupancy of the vacancy, and, for the fcc structure, appreciable binding enthalpies relative to the solution site have been found for occupancies of up to six. These extensions have been employed to model the depth distribution of ion-implanted hydrogen in Ni and Al during linear ramping of temperature, and the results have been used to interpret previously published data from these metals. The agreement between theory and experiment is good for both systems. In the case of Ni, the two experimentally observed hydrogen-release stages are both accounted for in terms of trapping at vacancies with a binding enthalpy that depends upon occupancy in accord with effective-medium theory

  3. Precipitation of metal sulphides using gaseous hydrogen sulphide: mathematical modelling

    NARCIS (Netherlands)

    Al Tarazi, M.Y.M.; Heesink, Albertus B.M.; Versteeg, Geert

    2004-01-01

    A mathematical model has been developed that describes the precipitation of metal sulffides in an aqueous solution containing two different heavy metal ions. The solution is assumed to consist of a well-mixed bulk and a boundary layer that is contacted with hydrogen sulphide gas. The model makes use

  4. Precipitation of metal sulphides using gaseous hydrogen sulphide : mathematical modelling

    NARCIS (Netherlands)

    Tarazi, Mousa Al-; Heesink, A. Bert M.; Versteeg, Geert F.

    2004-01-01

    A mathematical model has been developed that describes the precipitation of metal sulphides in an aqueous solution containing two different heavy metal ions. The solution is assumed to consist of a well-mixed bulk and a boundary layer that is contacted with hydrogen sulphide gas. The model makes use

  5. Standard practice for evaluation of hydrogen uptake, permeation, and transport in metals by an electrochemical technique

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1997-01-01

    1.1 This practice gives a procedure for the evaluation of hydrogen uptake, permeation, and transport in metals using an electrochemical technique which was developed by Devanathan and Stachurski. While this practice is primarily intended for laboratory use, such measurements have been conducted in field or plant applications. Therefore, with proper adaptations, this practice can also be applied to such situations. 1.2 This practice describes calculation of an effective diffusivity of hydrogen atoms in a metal and for distinguishing reversible and irreversible trapping. 1.3 This practice specifies the method for evaluating hydrogen uptake in metals based on the steady-state hydrogen flux. 1.4 This practice gives guidance on preparation of specimens, control and monitoring of the environmental variables, test procedures, and possible analyses of results. 1.5 This practice can be applied in principle to all metals and alloys which have a high solubility for hydrogen, and for which the hydrogen permeation is ...

  6. Borane-catalyzed cracking of C-C bonds in coal; Boran-katalysierte C-C-Bindungungsspaltung in Steinkohle

    Energy Technology Data Exchange (ETDEWEB)

    Narangerel, J; Haenel, M W [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-09-01

    Coal, especially coking coal, was reacted with hydrogen at comparatively mild reaction conditions (150-280 degrees centigrade, 20 MPa hydrogen pressure) in the presence of catalysts consisting of borange reagents and certain transition metal halides to obtaine more than 80 percent of pyridine-soluble products. The influence of the degree of coalification, catalyst and temperature on the borane-catalyzed hydrogenolysis of C-C bonds in coal was investigated. (orig.) [Deutsch] Steinkohlen, insbesondere im Inkohlungsbereich der Fettkohlen (Kokskohlen), werden in Gegenwart von Katalysatoren aus Boran-Reagentien und bestimmten Uebergangsmetallhalogeniden mit Wasserstoff bei vergleichsweise milden Reaktionsbedingungen (250-280 C, 20 MPa Wasserstoffdruck) in zu ueber 80% pyridinloesliche Produkte umgewandelt. Der Einfluss von Inkohlungsgrad, Katalysator und Temperatur auf die Boran-katalysierte C-C-Bindungshydrogenolyse in Kohle wurde untersucht. (orig.)

  7. Methodologies for hydrogen determination in metal oxides by prompt gamma activation analysis

    International Nuclear Information System (INIS)

    Alvarez, E.; Biegalski, S.R.; Landsberger, S.

    2007-01-01

    Prompt gamma activation analysis (PGAA), available at University of Texas at Austin (UT), has been employed for the direct determination of hydrogen content in a series of metal oxide materials typically used as cathodes in lithium ion battery systems. Special attention was given to the experimental setup including potential sources of error and system calibration for the detection of hydrogen. Spectral interference with hydrogen arising from cobalt was identified and corrected for. Limits of detection as a function of cobalt mass present in a given sample are also discussed. PGAA has proven to be a novel and precise technique for the determination of hydrogen in metal oxides. This type of investigation could provide valuable insight regarding the factors that limit the practical capacities of lithium ion oxide cathodes

  8. Complex Metal Hydrides for Hydrogen, Thermal and Electrochemical Energy Storage

    DEFF Research Database (Denmark)

    Moller, Kasper T.; Sheppard, Drew; Ravnsbaek, Dorthe B.

    2017-01-01

    Hydrogen has a very diverse chemistry and reacts with most other elements to form compounds, which have fascinating structures, compositions and properties. Complex metal hydrides are a rapidly expanding class of materials, approaching multi-functionality, in particular within the energy storage...... inspiration to solve the great challenge of our time: efficient conversion and large-scale storage of renewable energy....... field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...

  9. Microstructural studies of hydrogen and deuterium in bcc refractory metals. Final technical report

    International Nuclear Information System (INIS)

    Moss, S.C.

    1984-04-01

    Research was conducted on the microstructural atomic arrangements in alloys of hydrogen and deuterium with bcc refractory metals with emphasis on V and Nb. Because these are interstitial phases in which the host metal lattice is substantially deformed by the incorporation of the H(D) atoms, there are pronounced x-ray scattering effects. X-ray diffraction was used, with neutron scattering providing useful corollary data. One objective was to determine the phase relations, solid solution structures and phase transitions in metal-hydride alloys which depend upon the hydrogen-hydrogen interaction via the displacement field of the metal atoms. This has often included the elucidation of subtle thermodynamic properties (as in critical wetting) which are revealed in structural studies. Crystals were supplied for positron annihilation studies of the Fermi surface of H-Ta alloys which have revealed significant electronic trends. Work on alkali-graphite intercalates was initiated

  10. Tunable hydrogen storage in magnesium-transition metal compounds: first-principles calculations

    NARCIS (Netherlands)

    Er, S.; Tiwari, Dhirendra; Tiwari, D.; de Wijs, Gilles A.; Brocks, G.

    2009-01-01

    Magnesium dihydride (MgH2) stores 7.7 wt % hydrogen but it suffers from a high thermodynamic stability and slow (de)hydrogenation kinetics. Alloying Mg with lightweight transition metals (TM) (=Sc,Ti,V,Cr) aims at improving the thermodynamic and kinetic properties. We study the structure and

  11. Hydrogen diffusion and trapping in bcc and fcc metals

    International Nuclear Information System (INIS)

    Richter, D.

    1979-01-01

    The fundamental aspects of the metal--hydrogen systems are described. The large number of anomalous properties are the reason for continuous scientific effort. The time scale of hydrogen motion is extremely short. The characteristic frequencies of the localized modes of hydrogen in Ta, Nb, or V are in the order of 10 -14 sec (energies between 0.1 to 0.2 eV); the jump frequencies for H-diffusion at elevated temperatures in those systems are between 10 +12 to 10 +13 sec -1 . They are comparable with the correlation times for diffusion in liquids and more than ten orders of magnitude larger than the jump times for nitrogen in Nb. Out of the large number of experimental data this paper will survey only some recent results on representative fcc and bcc metals for dilute H solutions. The nature of the elementary step in H-diffusion is described. Here the temperature and isotope dependence of the H-diffusion coefficient gives hints to the mechanism involved. The experimental results are discussed in terms of semiclassical and quantum mechanical diffusion theories

  12. Kinetic Studies on Enzyme-Catalyzed Reactions: Oxidation of Glucose, Decomposition of Hydrogen Peroxide and Their Combination

    Science.gov (United States)

    Tao, Zhimin; Raffel, Ryan A.; Souid, Abdul-Kader; Goodisman, Jerry

    2009-01-01

    The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± 0.7) ×104 M−1s−1 at 37°C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37°C and well above unity at 25°C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s−1 and 0.090 s−1 respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain. PMID:19348778

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

    International Nuclear Information System (INIS)

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

    2010-01-01

    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

  14. 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

  15. Development of hydrogen oxidizing bacteria using hydrogen from radiolysis or metal corrosion

    International Nuclear Information System (INIS)

    Libert, M.F.; Sellier, R.; Marty, V.; Camaro, S.

    2000-01-01

    The effect of many parameters need to be studied to characterize the long term behavior of nuclear waste in a deep repository. These parameters concern the chemical effects, radiolytic effects, mechanical properties, water composition, and microbiological activity. To evaluate microbial activity in such an environment, work was focused on an inventory of key nutrients (C, H, 0, N, P, S) and energy sources required for bacterial growth. The production of hydrogen in the nuclear waste environment leads to the growth of hydrogen oxidizing bacteria, which modify the gas production balance. A deep repository containing bituminized waste drums implies several sources of hydrogen: - water radiolysis; -corrosion of metal containers; - radiolysis of the embedding matrix (bitumen). Two deep geological disposal conditions leading to H 2 production in a bituminized nuclear waste environment were simulated in the present study: - H 2 production by iron corrosion under anaerobic conditions was simulated by adding 10% of H 2 in the atmosphere; - H 2 production by radiolysis of bitumen matrix was approached by subjecting this material to external gamma irradiation with a dose rate near real conditions (6 Gy/h). The presence of dissolved H 2 in water allows the growth of hydrogen oxidizing bacteria leading to: - CO 2 and N 2 production; - H 2 consumption; - lower NO 3 - concentration caused by reduction to nitrogen. In the first case, hydrogen consumption is limited by the NO 3 - release rate from the bitumen matrix. In the second case, however, under gamma radiation at a low dose rate, hydrogen production is weak, and the hydrogen is completely consumed by microorganisms. Knowledge about these hydrogen oxidizing bacteria is just beginning to emerge. Heterotrophic denitrifying bacteria adapt well to hydrogen metabolism (autotrophic metabolism) by oxidizing H 2 instead of hydrocarbons. (authors)

  16. A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

    International Nuclear Information System (INIS)

    Lu, Jinlian; Guo, Yanhua; Zhang, Yun; Tang, Yingru; Cao, Juexian

    2015-01-01

    A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%, 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.

  17. 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.

  18. An electrochemical method for determining hydrogen concentrations in metals and some applications

    Science.gov (United States)

    Danford, M. D.

    1983-01-01

    An electrochemical method was developed for the determination of hydrogen in metals using the EG&G-PARC Model 350A Corrosion Measurement Console. The method was applied to hydrogen uptake, both during electrolysis and electroplating, and to studies of hydrogen elimination and the effect of heat treatment on elimination times. Results from these studies are presented.

  19. Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

    Science.gov (United States)

    Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

    2018-06-01

    Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

  20. Modeling hydrogen storage in boron-substituted graphene decorated with potassium metal atoms

    CSIR Research Space (South Africa)

    Tokarev, A

    2015-03-01

    Full Text Available Boron-substituted graphene decorated with potassium metal atoms was considered as a novel material for hydrogen storage. Density functional theory calculations were used to model key properties of the material, such as geometry, hydrogen packing...

  1. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  2. Radiative proton-capture nuclear processes in metallic hydrogen

    International Nuclear Information System (INIS)

    Ichimaru, Setsuo

    2001-01-01

    Protons being the lightest nuclei, metallic hydrogen may exhibit the features of quantum liquids most relevant to enormous enhancement of nuclear reactions; thermonuclear and pycnonuclear rates and associated enhancement factors of radiative proton captures of high-Z nuclei as well as of deuterons are evaluated. Atomic states of high-Z impurities are determined in a way consistent with the equations of state and screening characteristics of the metallic hydrogen. Rates of pycnonuclear p-d reactions are prodigiously high at densities ≥20 g/cm 3 , pressures ≥1 Gbar, and temperatures ≥950 K near the conditions of solidification. It is also predicted that proton captures of nuclei such as C, N, O, and F may take place at considerable rates, owing to strong screening by K-shell electrons, if the densities ≥60-80 g/cm 3 , the pressures ≥7-12 Gbar, and the temperatures just above solidification. The possibilities and significance of pycnonuclear p-d fusion experiments are specifically remarked

  3. A metal-catalyzed enyne-cyclization step for the synthesis of bi- and tricyclic scaffolds amenable to molecular library production

    DEFF Research Database (Denmark)

    Wu, Peng; Cohrt, Anders Emil O'Hanlon; Petersen, Rico

    2016-01-01

    A facile metal-catalyzed diversification step for the synthesis of novel bi- and tricyclic scaffolds from enyne substrates is reported in this study. From a single starting material, topologically diverse scaffolds for library synthesis can be generated and decorated in a few steps. The methodology...

  4. 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

  5. A calculation of the surface recombination rate constant for hydrogen isotopes on metals

    International Nuclear Information System (INIS)

    Baskes, M.J.

    1980-01-01

    The surface recombination rate constant for hydrogen isotopes on a metal has been calculated using a simple model whose parameters may be determined by direct experimental measurements. Using the experimental values for hydrogen diffusivity, solubility, and sticking coefficient at zero surface coverage a reasonable prediction of the surface recombination constant may be made. The calculated recombination constant is in excellent agreement with experiment for bcc iron. A heuristic argument is developed which, along with the rate constant calculation, shows that surface recombination is important in those metals in which hydrogen has an exothermic heat of solution. (orig.)

  6. Complex metal hydrides for hydrogen, thermal and electrochemical energy storage

    DEFF Research Database (Denmark)

    Møller, Kasper T.; Sheppard, Drew; Ravnsbæk, Dorthe B.

    2017-01-01

    field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...... how complex metal hydrides may act in an integrated setup with a fuel cell. This review focuses on the unique properties of light element complex metal hydrides mainly based on boron, nitrogen and aluminum, e.g., metal borohydrides and metal alanates. Our hope is that this review can provide new...

  7. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  8. Metal-mediated DNA base pairing: alternatives to hydrogen-bonded Watson-Crick base pairs.

    Science.gov (United States)

    Takezawa, Yusuke; Shionoya, Mitsuhiko

    2012-12-18

    With its capacity to store and transfer the genetic information within a sequence of monomers, DNA forms its central role in chemical evolution through replication and amplification. This elegant behavior is largely based on highly specific molecular recognition between nucleobases through the specific hydrogen bonds in the Watson-Crick base pairing system. While the native base pairs have been amazingly sophisticated through the long history of evolution, synthetic chemists have devoted considerable efforts to create alternative base pairing systems in recent decades. Most of these new systems were designed based on the shape complementarity of the pairs or the rearrangement of hydrogen-bonding patterns. We wondered whether metal coordination could serve as an alternative driving force for DNA base pairing and why hydrogen bonding was selected on Earth in the course of molecular evolution. Therefore, we envisioned an alternative design strategy: we replaced hydrogen bonding with another important scheme in biological systems, metal-coordination bonding. In this Account, we provide an overview of the chemistry of metal-mediated base pairing including basic concepts, molecular design, characteristic structures and properties, and possible applications of DNA-based molecular systems. We describe several examples of artificial metal-mediated base pairs, such as Cu(2+)-mediated hydroxypyridone base pair, H-Cu(2+)-H (where H denotes a hydroxypyridone-bearing nucleoside), developed by us and other researchers. To design the metallo-base pairs we carefully chose appropriate combinations of ligand-bearing nucleosides and metal ions. As expected from their stronger bonding through metal coordination, DNA duplexes possessing metallo-base pairs exhibited higher thermal stability than natural hydrogen-bonded DNAs. Furthermore, we could also use metal-mediated base pairs to construct or induce other high-order structures. These features could lead to metal-responsive functional

  9. Hydrogen storage alloys for nickel/metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Kuriyama, Nobuhiro; Sakai, Tetsuo; Myamura, Hiroshi; Tanaka, Hideaki; Ishikawa, Hiroshi; Uehara, Itsuki [Osaka National Research Inst. (Japan)

    1996-06-01

    Efforts to improve performance of metal hydride electrodes such as substitution of alloy components, heat treatment, and surface treatment intended to change surface and bulk structure of hydrogen storage alloys, mainly LaNi{sub 5} based alloys, are reviewed. The importance of control of morphology is emphasized. (author)

  10. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in

  11. Metal complex derivatives of hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Grohol, D.; Blinn, E.L.

    1994-01-01

    Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

  12. Cooperativity in Surface Bonding and Hydrogen Bonding of Water and Hydroxyl at Metal Surfaces

    DEFF Research Database (Denmark)

    Schiros, T.; Ogasawara, H.; Naslund, L. A.

    2010-01-01

    of the mixed phase at metal surfaces. The surface bonding can be considered to be similar to accepting a hydrogen bond, and we can thereby apply general cooperativity rules developed for hydrogen-bonded systems. This provides a simple understanding of why water molecules become more strongly bonded...... to the surface upon hydrogen bonding to OH and why the OH surface bonding is instead weakened through hydrogen bonding to water. We extend the application of this simple model to other observed cooperativity effects for pure water adsorption systems and H3O+ on metal surfaces.......We examine the balance of surface bonding and hydrogen bonding in the mixed OH + H2O overlayer on Pt(111), Cu(111), and Cu(110) via density functional theory calculations. We find that there is a cooperativity effect between surface bonding and hydrogen bonding that underlies the stability...

  13. Fe3O4 and metal-organic framework MIL-101(Fe) composites catalyze luminol chemiluminescence for sensitively sensing hydrogen peroxide and glucose.

    Science.gov (United States)

    Qian Tang, Xue; Dan Zhang, Yi; Wei Jiang, Zhong; Mei Wang, Dong; Zhi Huang, Cheng; Fang Li, Yuan

    2018-03-01

    In this work, Fe 3 O 4 and metal-organic framework MIL-101(Fe) composites (Fe 3 O 4 /MIL-101(Fe)) was demonstrated to possess excellent catalytic property to directly catalyze luminol chemiluminescence without extra oxidants. We utilized Fe 3 O 4 /MIL-101(Fe) to develop a ultra-sensitive quantitative analytical method for H 2 O 2 and glucose. The possible mechanism of the chemiluminescence reaction had been investigated. Under optimal conditions, the relative chemiluminescence intensity was linearly proportional to the logarithm of H 2 O 2 concentration in the range of 5-150nM with a limit of detection of 3.7nM (signal-to-noise ratio = 3), and glucose could be linearly detected in the range from 5 to 100nM and the detection limit was 4.9nM (signal-to-noise ratio = 3). Furthermore, the present approach was successfully applied to quantitative determination of H 2 O 2 in medical disinfectant and glucose in human serum samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Hydrogen in metals

    CSIR Research Space (South Africa)

    Carter, TJ

    2001-04-01

    Full Text Available .J. Cartera,*, L.A. Cornishb aAdvanced Engineering & Testing Services, MATTEK, CSIR, Private Bag X28, Auckland Park 2006, South Africa bSchool of Process and Materials Engineering, University of the Witwatersrand, Private Bag 3, P.O. WITS 2050, South Africa... are contrasted, and an unusual case study of hydrogen embrittlement of an alloy steel is presented. 7 2001 Published by Elsevier Science Ltd. Keywords: Hydrogen; Hydrogen-assisted cracking; Hydrogen damage; Hydrogen embrittlement 1. Introduction Hydrogen suC128...

  15. High Density Hydrogen Storage in Metal Hydride Composites with Air Cooling

    OpenAIRE

    Dieterich, Mila; Bürger, Inga; Linder, Marc

    2015-01-01

    INTRODUCTION In order to combine fluctuating renewable energy sources with the actual demand of electrical energy, storages are essential. The surplus energy can be stored as hydrogen to be used either for mobile use, chemical synthesis or reconversion when needed. One possibility to store the hydrogen gas at high volumetric densities, moderate temperatures and low pressures is based on a chemical reaction with metal hydrides. Such storages must be able to absorb and desorb the hydrogen qu...

  16. 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

    2017-04-19

    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 was evaluated.

  17. Synthesis of hexahydropyrrolo[2,1-a]isoquinoline compound libraries through a Pictet–Spengler cyclization/metal-catalyzed cross coupling/amidation sequence

    DEFF Research Database (Denmark)

    Petersen, Rico; Cohrt, A. Emil; Petersen, Michael Åxman

    2015-01-01

    incorporating two handles for diversification, were synthesized through an oxidative cleavage/Pictet–Spengler reaction sequence in high overall yields. A subsequent metal-catalyzed cross coupling/amidation protocol was developed and its utility in library synthesis was validated by construction of a 20-membered...

  18. Oxidation of Phenol by Hydrogen Peroxide Catalyzed by Metal-Containing Poly(amidoxime Grafted Starch

    Directory of Open Access Journals (Sweden)

    Hany El-Hamshary

    2011-11-01

    Full Text Available Polyamidoxime chelating resin was obtained from polyacrylonitrile (PAN grafted starch. The nitrile groups of the starch-grafted polyacrylonitrile (St-g-PAN were converted into amidoximes by reaction with hydroxylamine under basic conditions. The synthesized graft copolymer and polyamidoxime were characterized by FTIR, TGA and elemental microanalysis. Metal chelation of the polyamidoxime resin with iron, copper and zinc has been studied. The produced metal-polyamidoxime polymer complexes were used as catalysts for the oxidation of phenol using H2O2 as oxidizing agent. The oxidation of phenol depends on the central metal ion present in the polyamidoxime complex. Reuse of M-polyamidoxime catalyst/H2O2 system showed a slight decrease in catalytic activities for all M-polyamidoxime catalysts.

  19. Development of the work function approach to the underpotential deposition of metals. Application to the hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Trasatti, S.

    1975-01-01

    A theory is developed for the underpotential deposition of metals. Concepts are then extended to oxygen and hydrogen adsorption. Analysis of results shows that, unlike oxygen adsorption, hydrogen adsorption in solution probably follows a different pattern with respect to the gas phase situation. The hydrogen evolution reaction is discussed in the light of the above findings and it is shown that usual concepts regarding the reactivity scale of metals towards hydrogen should be reconsidered taking into account solvent and entropy effects. The latters can account for the behaviour of sp-metals. The formers are important with transition metals. The final picture is consistent with the idea that M-H 2 O interactions are much stronger on transition than on sp-metals. (orig.) [de

  20. Hydrogen evolution on nano-particulate transition metal sulfides

    DEFF Research Database (Denmark)

    Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.

    2008-01-01

    The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal sul...

  1. Nanoporous, Metal Carbide, Surface Diffusion Membranes for High Temperature Hydrogen Separations

    Energy Technology Data Exchange (ETDEWEB)

    Way, J. Douglas [Colorado School of Mines, Golden, CO (United States). Dept. of Chemical and Biological Engineering; Wolden, Colin A. [Colorado School of Mines, Golden, CO (United States)

    2013-09-30

    Colorado School of Mines (CSM) developed high temperature, hydrogen permeable membranes that contain no platinum group metals with the goal of separating hydrogen from gas mixtures representative of gasification of carbon feedstocks such as coal or biomass in order to meet DOE NETL 2015 hydrogen membrane performance targets. We employed a dual synthesis strategy centered on transition metal carbides. In the first approach, novel, high temperature, surface diffusion membranes based on nanoporous Mo2C were fabricated on ceramic supports. These were produced in a two step process that consisted of molybdenum oxide deposition followed by thermal carburization. Our best Mo2C surface diffusion membrane achieved a pure hydrogen flux of 367 SCFH/ft2 at a feed pressure of only 20 psig. The highest H2/N2 selectivity obtained with this approach was 4.9. A transport model using “dusty gas” theory was derived to describe the hydrogen transport in the Mo2C coated, surface diffusion membranes. The second class of membranes developed were dense metal foils of BCC metals such as vanadium coated with thin (< 60 nm) Mo2C catalyst layers. We have fabricated a Mo2C/V composite membrane that in pure gas testing delivered a H2 flux of 238 SCFH/ft2 at 600 °C and 100 psig, with no detectable He permeance. This exceeds the 2010 DOE Target flux. This flux is 2.8 times that of pure Pd at the same membrane thickness and test conditions and over 79% of the 2015 flux target. In mixed gas testing we achieved a permeate purity of ≥99.99%, satisfying the permeate purity milestone, but the hydrogen permeance was low, ~0.2 SCFH/ft2.psi. However, during testing of a Mo2C coated Pd alloy membrane with DOE 1 feed gas mixture a hydrogen permeance of >2 SCFH/ft2.psi was obtained which was stable during the entire test, meeting the permeance associated with

  2. Experimental Challenges in Studying Hydrogen Absorption in Ultrasmall Metal Nanoparticles

    International Nuclear Information System (INIS)

    Zlotea, Claudia; Oumellal, Yassine; Provost, Karine; Ghimbeu, Camelia Matei

    2016-01-01

    Recent advances on synthesis, characterization, and hydrogen absorption properties of ultrasmall metal nanoparticles (defined here as objects with average size ≤3 nm) are briefly reviewed in the first part of this work. The experimental challenges encountered in performing accurate measurements of hydrogen absorption in Mg- and noble metal-based ultrasmall nanoparticles are addressed. The second part of this work reports original results obtained for ultrasmall bulk-immiscible Pd–Rh nanoparticles. Carbon-supported Pd–Rh nanoalloys in the whole binary chemical composition range have been successfully prepared by liquid impregnation method followed by reduction at 300°C. EXAFS investigations suggested that the local structure of these nanoalloys is partially segregated into Rh-rich core and Pd-rich surface coexisting within the same nanoparticles. Downsizing to ultrasmall dimensions completely suppresses the hydride formation in Pd-rich nanoalloys at ambient conditions, contrary to bulk and larger nanosized (5–6 nm) counterparts. The ultrasmall Pd 90 Rh 10 nanoalloy can absorb hydrogen-forming solid solutions under these conditions, as suggested by in situ X-ray diffraction (XRD). Apart from this composition, common laboratory techniques, such as in situ XRD, DSC, and PCI, failed to clarify the hydrogen interaction mechanism: either adsorption on developed surfaces or both adsorption and absorption with formation of solid solutions. Concluding insights were brought by in situ EXAFS experiments at synchrotron: ultrasmall Pd 75 Rh 25 and Pd 50 Rh 50 nanoalloys absorb hydrogen-forming solid solutions at ambient conditions. Moreover, the hydrogen solubility in these solid solutions is higher with increasing Pd content, and this trend can be understood in terms of hydrogen preferential occupation in the Pd-rich regions, as suggested by in situ EXAFS. The Rh-rich nanoalloys (Pd 25 Rh 75 and Pd 10 Rh 90 ) only adsorb hydrogen on the developed surface of ultrasmall

  3. Theoretical study on platinum-catalyzed isotope exchange reaction mechanism of hydrogen and liquid water

    International Nuclear Information System (INIS)

    Hu Sheng; Wang Heyi; Luo Shunzhong

    2009-04-01

    Based on electron and vibration approximate means and the density function theory B3LYP, the ΔG degree and equilibrium pressures of adsorption and dissociation reactions of H 2 and water vapor on Pt surface have been calculated. The adsorption, dissociation and coadsorption actions of H 2 and water were analyzed. According to the ΔG degree, hydrogen molecule combines with metal atoms in single atom, and water vapor molecule has no tendency to dissociate on Pt surface. The dissociation of hydrogen molecule would hold back the direct adsorption of water vapor molecules on Pt surface. The structures of Pt-H (OH 2 ) n + (n=1, 2, 3) hydroniums were optimized. According to the mulliken overlap populations, Pt-H (OH 2 ) + is not stable or produced. Hydrogen isotope exchange occurs between hydration layer and D atoms which adsorb on Pt surface via intermediates (H 2 O) n D + (ads) (n≥2). (authors)

  4. Iridium‐Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Madsen, Robert

    2012-01-01

    A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe=cyclooct......A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe...... to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation...

  5. Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis.

    Science.gov (United States)

    Kou, K G M; Dong, V M

    2015-06-07

    Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. A detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified.

  6. Cascades for hydrogen isotope separation using metal hydrides

    International Nuclear Information System (INIS)

    Hill, F.B.; Grzetic, V.

    1982-01-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes

  7. Cascades for hydrogen isotope separation using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Hill, F B; Grzetic, V [Brookhaven National Lab., Upton, NY (USA)

    1983-02-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes.

  8. Applications of some microscopic, diffraction and absorption techniques to the study of metal--hydrogen systems

    International Nuclear Information System (INIS)

    Pick, M.A.

    1979-01-01

    Several experimental techniques were reviewed which are used to investigate metal hydrogen systems. The first technique is metallography and optical microscopy. This is a very old technique which was found to be very powerful in the case of metal hydrogen systems. A few examples of such work are shown and the results are discussed

  9. Indirect, reversible high-density hydrogen storage in compact metal ammine salts

    DEFF Research Database (Denmark)

    Sørensen, Rasmus Zink; Hummelshøj, Jens Strabo; Klerke, Asbjørn

    2008-01-01

    The indirect hydrogen storage capabilities of Mg(NH3)(6)Cl-2, Ca(NH3)(6)Cl-2, Mn(NH3)(6)Cl-2, and Ni(NH3)(6)Cl-2 are investigated. All four metal ammine chlorides can be compacted to solid tablets with densities of at least 95% of the crystal density. This gives very high indirect hydrogen...

  10. A fast response hydrogen sensor with Pd metallic grating onto a fiber's end-face

    Science.gov (United States)

    Yan, Haitao; Zhao, Xiaoyan; Zhang, Chao; Li, Qiu-Ze; Cao, Jingxiao; Han, Dao-Fu; Hao, Hui; Wang, Ming

    2016-01-01

    We demonstrated an integrated hydrogen sensor with Pd metallic grating fabricated on a fiber end-face. The grating consists of three thin metal layers in stacks, Au, WO3 and Pd. The WO3 is used as a waveguide layer between the Pd and Au layer. The Pd layer is etched by using a focused ion beam (FIB) method, forming a Pd metallic grating with period of 450 nm. The sensor is experimentally exposed to hydrogen gas environment. Changing the concentration from 0% to 4% which is the low explosive limit (LEL), the resonant wavelength measured from the reflection experienced 28.10 nm spectral changes in the visible range. The results demonstrated that the sensor is sensitive for hydrogen detection and it has fast response and low temperature effect.

  11. Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter

    2003-07-01

    The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and carbon containing alloys

  12. Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter

    2003-07-01

    The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and

  13. Hydrogen storage by reaction between metallic amides and imides

    International Nuclear Information System (INIS)

    Eymery, J.B.; Cahen, S.; Tarascon, J.M.; Janot, R.

    2007-01-01

    This paper details the various metal-N-H systems reported in the literature as possible hydrogen storage materials. In a first part, we discuss the hydrogen storage performances of the Li-N-H system and the desorption mechanism of the LiH-LiNH 2 mixture is especially presented. The possibility of storing hydrogen using two other binary systems (Mg-N-H and Ca-N-H) is described in a second part. In the third part of the paper, we discuss about the performances of the highly promising Li-Mg-N-H system, for which a nice reversibility is obtained at 200 C with an experimental hydrogen capacity of about 5.0 wt.%. Other ternary systems, as Li-B-N-H and Li-Al-N-H, are presented in the last part of this review paper. We especially emphasize the performances obtained in our Laboratory at Amiens with a LiAl(NH 2 ) 4 -LiH mixture able to desorb around 6.0 wt.% of hydrogen at only 130 C. (authors)

  14. N-Alkylation by Hydrogen Autotransfer Reactions.

    Science.gov (United States)

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  15. Permeation of hydrogen through metal membranes

    International Nuclear Information System (INIS)

    Wienhold, P.; Rota, E.; Waelbroeck, F.; Winter, J.; Banno, Tatsuya.

    1986-08-01

    Experiments show that the permeant flux of hydrogen through a metal membrane at low driving pressures ( r is introduced into the model as a new material constant and the rate equations are given. After the description of the wall pump effect, a variety of different limiting cases are discussed for a symmetrical permeation membrane. This is modified to the asymmetric case and to the influence of particle implantation. The permeation number W turns out to be a dimensionless quantity which characterizes the permeation range and predicts the permeant flux in steady state. (orig.)

  16. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  17. Transition Metal Catalyzed Reactions of Carbohydrates: a Nonoxidative Approach to Oxygenated Organics

    Energy Technology Data Exchange (ETDEWEB)

    Andrews, Mark

    1997-01-08

    There is a critical need for new environmentally friendly processes in the United States chemical industry as legislative and economic pressures push the industry to zero-waste and cradle-to-grave responsibility for the products they produce. Carbohydrates represent a plentiful, renewable resource, which for some processes might economically replace fossil feedstocks. While the conversion of biomass to fuels, is still not generally economical, the selective synthesis of a commodity or fine chemical, however, could compete effectively if appropriate catalytic conversion systems can be found. Oxygenated organics, found in a variety of products such as nylon and polyester, are particularly attractive targets. We believe that with concerted research efforts, homogeneous transition metal catalyzed reactions could play a significant role in bringing about this future green chemistry technology.

  18. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    KAUST Repository

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  19. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    KAUST Repository

    Takanabe, Kazuhiro; Isimjan, Tayirjan; Yu, Weili; Del Gobbo, Silvano; Xu, Wei

    2015-01-01

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  20. Luminescent chemical waves in the Cu(II)-catalyzed oscillatory oxidation of SCN- ions with hydrogen peroxide.

    Science.gov (United States)

    Pekala, Katarzyna; Jurczakowski, Rafał; Lewera, Adam; Orlik, Marek

    2007-05-10

    The oscillatory oxidation of thiocyanate ions with hydrogen peroxide, catalyzed by Cu2+ ions in alkaline media, was so far observed as occurring simultaneously in the entire space of the batch or flow reactor. We performed this reaction for the first time in the thin-layer reactor and observed the spatiotemporal course of the above process, in the presence of luminol as the chemiluminescent indicator. A series of luminescent patterns periodically starting from the random reaction center and spreading throughout the entire solution layer was reported. For a batch-stirred system, the bursts of luminescence were found to correlate with the steep decreases of the oscillating Pt electrode potential. These novel results open possibilities for further experimental and theoretical investigations of those spatiotemporal patterns, including studies of the mechanism of this chemically complex process.

  1. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    Grodkowski, J.

    2004-01-01

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  2. On the Hydrogen Cyanide Removal from Air using Metal loaded Polyacrylonitrile Composite Nanofibers

    Directory of Open Access Journals (Sweden)

    Bozorgmehr Maddah

    2017-12-01

    Full Text Available The present study highlights the potential application of electrospun polyacrylonitrile/metal salts (CrO3, CuCO3 nanofibrous filter media impregnated with TEDA (PAN-M-TEDA as an efficient adsorbent for hydrogen cyanide removal from air. The PAN-M-TEDA nanofiber before and after adsorption of hydrogen cyanide was characterized with Fourier transform infrared microscopy (FTIR. The concentration of hydrogen cyanide passes through the samples was determined by measuring the absorption of hydrogen cyanide in the solution containing indicator via UV-Vis spectroscopy. The results showed that introducing metal salts to PAN nanofiber along with their impregnation with TEDA, significantly increases the adsorption capacity of nanofibrous filter media. The adsorption of hydrogen cyanide over PAN-M-TEDA nanofiber was also studied as a function of thickness, PAN concentration and TEDA concentration by response surface methodology (RSM based on central composite design. It is found that the highest adsorption capacity can be achieved at thickness 28.42 mm, PAN concentration 16.19 w/v % and TEDA concentration 14.80 w/v %.

  3. 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.

  4. Metal oxide/hydrogen secondary battery; Kinzoku sankabutsu/suiso niji denchi

    Energy Technology Data Exchange (ETDEWEB)

    Hosobuchi, H.; Ema, M.

    1995-12-12

    Since the shape of powder produced by crushing the hydrogen storage alloy containing rare earth element varies widely, the density of the negative electrode made by packing the alloy powder is low. As a result, the secondary battery employing this negative electrode has a small discharge capacity. This invention solves the problem. Employing the hydrogen storage alloy containing rare earth element composed of particle shape of aspect ratio, A, of over 1.0 and below 3.0 gives rise to the negative electrode with high packing density, improving the discharge capacity of the metal oxide - hydrogen secondary battery. The more the shape of powder of hydrogen storage alloy containing rare earth element is near to sphere, the higher the packing density of negative electrode made of the hydrogen storage alloy containing rare earth element becomes. The preferable aspect ratio, A, of the powder is 1.0 {le} A {le} 2.0. Such alloy powder can be produced by mechanically grinding the rare-earth-element-containing hydrogen alloy ingot, or grinding by hydration, or grinding by atomizing followed by sieving. 1 fig., 1 tab.

  5. Hydrogen production during processing of radioactive sludge containing noble metals

    International Nuclear Information System (INIS)

    Ha, B.C.; Ferrara, D.M.; Bibler, N.E.

    1992-01-01

    Hydrogen was produced when radioactive sludge from Savannah River Site radioactive waste containing noble metals was reacted with formic acid. This will occur in a process tank in the Defense Waste Facility at SRS when waste is vitrified. Radioactive sludges from four tanks were tested in a lab-scale apparatus. Maximum hydrogen generation rates varied from 5 x10 -7 g H 2 /hr/g of sludge from the least reactive sludge (from Waste Tank 51) to 2 x10 -4 g H 2 /hr/g of sludge from the most reactive sludge (from Waste Tank 11). The time required for the hydrogen generation to reach a maximum varied from 4.1 to 25 hours. In addition to hydrogen, carbon dioxide and nitrous oxide were produced and the pH of the reaction slurry increased. In all cases, the carbon dioxide and nitrous oxide were generated before the hydrogen. The results are in agreement with large-scale studies using simulated sludges

  6. High pressure deuterium-tritium gas target vessels for muon-catalyzed fusion experiments

    International Nuclear Information System (INIS)

    Caffrey, A.J.; Spaletta, H.W.; Ware, A.G.; Zabriskie, J.M.; Hardwick, D.A.; Maltrud, H.R.; Paciotti, M.A.

    1989-01-01

    In experimental studies of muon-catalyzed fusion, the density of the hydrogen gas mixture is an important parameter. Catalysis of up to 150 fusions per muon has been observed in deuterium-tritium gas mixtures at liquid hydrogen density; at room temperature, such densities require a target gas pressure of the order of 1000 atmospheres (100 MPa, 15,000 psi). We report here the design considerations for hydrogen gas target vessels for muon-catalyzed fusion experiments that operate at 1000 and 10,000 atmospheres. The 1000 atmosphere high pressure target vessels are fabricated of Type A-286 stainless steel and lined with oxygen-free, high-conductivity (OFHC) copper to provide a barrier to hydrogen permeation of the stainless steel. The 10,000 atmosphere ultrahigh pressure target vessels are made from 18Ni (200 grade) maraging steel and are lined with OFHC copper, again to prevent hydrogen permeation of the steel. In addition to target design features, operating requirements, fabrication procedures, and secondary containment are discussed. 13 refs., 3 figs., 1 tab

  7. Metal-loaded SBA-16-like silica – Correlation between basicity and affinity towards hydrogen

    International Nuclear Information System (INIS)

    Ouargli-Saker, R.; Bouazizi, N.; Boukoussa, B.; Barrimo, Diana; Paola-Nunes-Beltrao, Ana; Azzouz, A.

    2017-01-01

    Highlights: • Metal dispersion in longitudinal channels confers adsorption properties to SBA-16. • Both Fe"0-NPs and Cu"0-NPs seem to be responsible of this effect. • Effect of the repetitive adsorption-desorption cycles on CO_2 and water sorption. • Hydrogen storage on the functionalized materials. - Abstract: Nanoparticles of Cu"o (CuNPs) and Fe"o (FeNPs) were dispersed in SBA-16-like silica, resulting metal-loaded materials (Cu-SBA-16 and Fe-SBA-16) with improved affinity towards hydrogen. Electron microscopy and X-ray diffraction showed that MNP dispersion occurs mainly inside SBA-16 channels. MNP incorporation was found to confer affinity to the silica surface, since higher CO_2 retention capacity (CRC) was registered Cu/SBA-16 and Fe/SBA-16. This was accompanied by a significant improvement of the affinity towards hydrogen, as supported by hydrogen adsorption tests. This was explained in terms of strong hydrogen interaction with MNP and lattice oxygen atoms. The results reported herein open new prospects for SBA-16 as potential adsorbents for hydrogen storage.

  8. Metal-loaded SBA-16-like silica – Correlation between basicity and affinity towards hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Ouargli-Saker, R. [Department of Materials Engineering, University of Science and Technology, El M’naouer, BP 1505, Oran (Algeria); Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C3P8 (Canada); Bouazizi, N. [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C3P8 (Canada); Unité de recherche, Electrochimie, Matériaux et Environnement, Faculté des Sciences de Gabès, Université de Gabès, Cité Erriadh, 6072 Gabès (Tunisia); Boukoussa, B. [Department of Materials Engineering, University of Science and Technology, El M’naouer, BP 1505, Oran (Algeria); Lqamb, Laboratório de Química Analítica Ambiental, Faculdade de Química, Pontifícia Universidade Católica do Rio Grande do Sul (Brazil); Barrimo, Diana [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C3P8 (Canada); Paola-Nunes-Beltrao, Ana [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C3P8 (Canada); Laboratory of Materials Chemistry L.C.M, University of Oran1 Ahmed Ben Bella, BP 1524, El-Mnaouer, 31000 Oran (Algeria); Azzouz, A., E-mail: azzouz.a@uqam.ca [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C3P8 (Canada)

    2017-07-31

    Highlights: • Metal dispersion in longitudinal channels confers adsorption properties to SBA-16. • Both Fe{sup 0}-NPs and Cu{sup 0}-NPs seem to be responsible of this effect. • Effect of the repetitive adsorption-desorption cycles on CO{sub 2} and water sorption. • Hydrogen storage on the functionalized materials. - Abstract: Nanoparticles of Cu{sup o} (CuNPs) and Fe{sup o} (FeNPs) were dispersed in SBA-16-like silica, resulting metal-loaded materials (Cu-SBA-16 and Fe-SBA-16) with improved affinity towards hydrogen. Electron microscopy and X-ray diffraction showed that MNP dispersion occurs mainly inside SBA-16 channels. MNP incorporation was found to confer affinity to the silica surface, since higher CO{sub 2} retention capacity (CRC) was registered Cu/SBA-16 and Fe/SBA-16. This was accompanied by a significant improvement of the affinity towards hydrogen, as supported by hydrogen adsorption tests. This was explained in terms of strong hydrogen interaction with MNP and lattice oxygen atoms. The results reported herein open new prospects for SBA-16 as potential adsorbents for hydrogen storage.

  9. Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Azofra, Luis Miguel; Jang, Yoon Kyung; Cavallo, Luigi; Rueping, Magnus

    2017-01-01

    An iron-catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non-innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran.

  10. Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling

    KAUST Repository

    El-Sepelgy, Osama

    2017-09-26

    An iron-catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non-innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran.

  11. Teaching - methodical and research center of hydrogen power engineering and platinum group metals in the former Soviet Union countries

    International Nuclear Information System (INIS)

    Evdokimov, A.A; Sigov, A.S; Shinkarenko, V.V.

    2005-01-01

    Full text: Teaching - Methodical and Research Center (TMRC) 'Sokolinaja Gora' is founded in order to provide methodical-information and scientific support of institutes of higher education in the field of hydrogen power engineering and platinum group metals in Russia and in the countries of the Former Soviet union. It is independent association of creative communities of scientist of higher educational specialists. The main directions of the Center activity are: 1. Teaching-methodological support and development of teaching in the field of hydrogen power engineering and platinum group metals in Russia in the countries of the Former Soviet Union. Themes of teaching includes the basic of safe using of hydrogen technologies and devices, ecological, economic and law aspects of new hydrogen power engineering, transition to which in 21 century is one of the central problems of mankind survival; 2. Organizing of joint researches by independent creative communities of scientists in the field of hydrogen power engineering and platinum group metal; 3. Independent scientific examination, which is made by Advisory Committee of High Technologies consisting of representatives of the countries of Former Soviet Union, which are standing participants of an Annual International Symposia 'Hydrogen Power Engineering and Platinum Group Metals in the Former Soviet Union Countries'. Structure of the Center: 1. Center of strategic development in the field of high technologies; 2. Scientific Research Institute of Hydrogen Power Engineering and Platinum Group Metals; 3. Teaching-Methodical Association in specialization 'Hydrogen Power Engineering and economics' and hydrogen wide spread training; 4. Media Center 'Hydrogen Power Engineering and Platinum Group Metals', 5. Organizational Center; 6. Administrative Center. The Center will be established step-by-step in 2005-2010 on the basis of the following programs: Teaching-methodological program. On the basis of this program it is planned to

  12. Empirical Method to Estimate Hydrogen Embrittlement of Metals as a Function of Hydrogen Gas Pressure at Constant Temperature

    Science.gov (United States)

    Lee, Jonathan A.

    2010-01-01

    High pressure Hydrogen (H) gas has been known to have a deleterious effect on the mechanical properties of certain metals, particularly, the notched tensile strength, fracture toughness and ductility. The ratio of these properties in Hydrogen as compared to Helium or Air is called the Hydrogen Environment Embrittlement (HEE) Index, which is a useful method to classify the severity of H embrittlement and to aid in the material screening and selection for safety usage H gas environment. A comprehensive world-wide database compilation, in the past 50 years, has shown that the HEE index is mostly collected at two conveniently high H pressure points of 5 ksi and 10 ksi near room temperature. Since H embrittlement is directly related to pressure, the lack of HEE index at other pressure points has posed a technical problem for the designers to select appropriate materials at a specific H pressure for various applications in aerospace, alternate and renewable energy sectors for an emerging hydrogen economy. Based on the Power-Law mathematical relationship, an empirical method to accurately predict the HEE index, as a function of H pressure at constant temperature, is presented with a brief review on Sievert's law for gas-metal absorption.

  13. The initial stages of the reaction between ZrCo and hydrogen studied by hot-stage microscopy

    International Nuclear Information System (INIS)

    Bloch, J.; Brill, M.; Ben-Eliahu, Y.; Gavra, Z.

    1998-01-01

    The development of hydride phase on the surface of ZrCo under 1 bar of hydrogen was investigated at temperatures between 75 and 300 C. Both surface modifications of the parent alloy and the nucleation and growth of hydride phase were observed. Surface modifications included: grain boundary outgrowth, intra-granular precipitation in the form of fine lamellar hydride phase and micro cracks. It is suggested that the surface modifications result from a combination of hydrogen solubility and the parent metal ductility. These modifications were enhanced near areas which had been previously transformed. The nucleation was self catalyzed, with new nuclei preferentially formed at the vicinity of growing former nuclei. All this suggested that the transport of hydrogen through the hydride phase is faster than its transfer through the surface passivation layer. The growth rate of the nuclei was similar to that of uranium. The activation energy for the growth was E a =24±3 kJ/mol. The results were compared with several other metal-hydrogen systems. It is suggested that the important physical factors controlling the mechanism of the initial hydriding reaction are hydrogen solubility and the brittleness of the parent metal/alloy. These parameters are responsible to the different changes observed during the initial hydriding stages which include: surface modifications, cracking, nucleation and growth. (orig.)

  14. Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

    Energy Technology Data Exchange (ETDEWEB)

    Horn, G; Frohning, C D; Cornils, B [Ruhrchemie A.G., Oberhausen (Germany, F.R.)

    1976-07-01

    The special properties of the six platinum group elements - ruthenium, rhodium, palladium, osmium, iridium, platinum - make them useful as active metals for catalytic reactions. Especially valuable is their property of favouring a single reaction even when the possibility of a number of parallel reactions exists under certain reaction conditions. This selectivity of the noble metal catalyst may be directed or enhanced through appropriate choise of the metal, the reaction conditions, the duration of the reaction, the amount of hydrogen etc. Even the physical state of the catalyst - supported or unsupported - is of influence when using noble metal catalysts as described in this report.

  15. Metal organoclays with compacted structure for truly physical capture of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Tahir, M. Nazir; Sennour, Radia [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C 3P8 QC (Canada); Arus, Vasilica Alisa [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C 3P8 QC (Canada); Catalysis and Microporous Materials Laboratory, Vasile-Alecsandri University of Bacau, 600115 (Romania); Sallam, Lamyaa M. [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C 3P8 QC (Canada); Roy, René, E-mail: roy.rene@uqam.ca [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C 3P8 QC (Canada); Azzouz, Abdelkrim, E-mail: azzouz.a@uqam.ca [Nanoqam, Department of Chemistry, University of Quebec at Montreal, H3C 3P8 QC (Canada)

    2017-03-15

    Highlights: • Functionalization of thio-dendrons onto montmorillonite clay. • Incorporation and stabilization of PdNP in to the functionalized clays. • Role of −S:Pd and −O:Pd interactions in NP dispersion and stabilization. • Applications of PdNP incorporated modified clays for physical adsorption of H{sub 2}. - Abstract: Truly reversible capture of hydrogen was achieved at ambient conditions on Pd-loaded organo-montmorillonites obtained by photo-addition of different thiols on propargylated-TRIS cations already grafted on the clay surface. TEM insights showed that more than 90% of Pd{sup 0} incorporated occur as 0.3–0.5 nm subnanoparticles (PdSNPs). XPS and NMR analyses revealed simultaneous strong S:Pd{sup 0} and O:Pd{sup 0} interactions that ”cement” the organic moiety around PdSNPs. The significant decrease in porosity suggests a compacted structure that impedes not only metal aggregation, but also hydrogen diffusion in the metal bulk. Thus, hydrogen appears to adsorb mainly via physical condensation around PdSNPs. These thiol-clay matrices showed hydrogen surface affinity factors of up to 0.51 mmol m{sup −2} at ambient temperature and pressure. This is higher than those reported for much more sophisticated materials. DSC measurements showed very low desorption heat between 20 and 80 °C. Hydrogen release was achieved merely under vacuum or slight heating starting from 40 °C and was almost completed up to 85 °C. This provides a proof of concept of truly reversible capture of hydrogen for concentration and/or storage purposes. Such a performance has never been achieved at ambient temperature and pressure. These findings open new prospects to develop low-cost materials for reversible hydrogen storage without energy and safety constraints.

  16. Metal organoclays with compacted structure for truly physical capture of hydrogen

    International Nuclear Information System (INIS)

    Tahir, M. Nazir; Sennour, Radia; Arus, Vasilica Alisa; Sallam, Lamyaa M.; Roy, René; Azzouz, Abdelkrim

    2017-01-01

    Highlights: • Functionalization of thio-dendrons onto montmorillonite clay. • Incorporation and stabilization of PdNP in to the functionalized clays. • Role of −S:Pd and −O:Pd interactions in NP dispersion and stabilization. • Applications of PdNP incorporated modified clays for physical adsorption of H_2. - Abstract: Truly reversible capture of hydrogen was achieved at ambient conditions on Pd-loaded organo-montmorillonites obtained by photo-addition of different thiols on propargylated-TRIS cations already grafted on the clay surface. TEM insights showed that more than 90% of Pd"0 incorporated occur as 0.3–0.5 nm subnanoparticles (PdSNPs). XPS and NMR analyses revealed simultaneous strong S:Pd"0 and O:Pd"0 interactions that ”cement” the organic moiety around PdSNPs. The significant decrease in porosity suggests a compacted structure that impedes not only metal aggregation, but also hydrogen diffusion in the metal bulk. Thus, hydrogen appears to adsorb mainly via physical condensation around PdSNPs. These thiol-clay matrices showed hydrogen surface affinity factors of up to 0.51 mmol m"−"2 at ambient temperature and pressure. This is higher than those reported for much more sophisticated materials. DSC measurements showed very low desorption heat between 20 and 80 °C. Hydrogen release was achieved merely under vacuum or slight heating starting from 40 °C and was almost completed up to 85 °C. This provides a proof of concept of truly reversible capture of hydrogen for concentration and/or storage purposes. Such a performance has never been achieved at ambient temperature and pressure. These findings open new prospects to develop low-cost materials for reversible hydrogen storage without energy and safety constraints.

  17. Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

    Directory of Open Access Journals (Sweden)

    Yasuharu Kanda

    2018-04-01

    Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

  18. Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery- Part 2: Cells with Metal Hydride Storage.

    Science.gov (United States)

    Purushothaman, B K; Wainright, J S

    2012-05-15

    A sub-atmospheric pressure nickel hydrogen (Ni-H(2)) battery with metal hydride for hydrogen storage is developed for implantable neuroprosthetic devices. Pressure variations during charge and discharge of the cell are analyzed at different states of charge and are found to follow the desorption curve of the pressure composition isotherm (PCI) of the metal hydride. The measured pressure agreed well with the calculated theoretical pressure based on the PCI and is used to predict the state of charge of the battery. Hydrogen equilibration with the metal hydride during charge/discharge cycling is fast when the pressure is in the range from 8 to 13 psia and slower in the range from 6 to 8 psia. The time constant for the slower hydrogen equilibration, 1.37h, is similar to the time constant for oxygen recombination and therefore pressure changes due to different mechanisms are difficult to estimate. The self-discharge rate of the cell with metal hydride is two times lower in comparison to the cell with gaseous hydrogen storage alone and is a result of the lower pressure in the cell when the metal hydride is used.

  19. Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery– Part 2: Cells with Metal Hydride Storage

    Science.gov (United States)

    Purushothaman, B. K.; Wainright, J. S.

    2012-01-01

    A sub-atmospheric pressure nickel hydrogen (Ni-H2) battery with metal hydride for hydrogen storage is developed for implantable neuroprosthetic devices. Pressure variations during charge and discharge of the cell are analyzed at different states of charge and are found to follow the desorption curve of the pressure composition isotherm (PCI) of the metal hydride. The measured pressure agreed well with the calculated theoretical pressure based on the PCI and is used to predict the state of charge of the battery. Hydrogen equilibration with the metal hydride during charge/discharge cycling is fast when the pressure is in the range from 8 to 13 psia and slower in the range from 6 to 8 psia. The time constant for the slower hydrogen equilibration, 1.37h, is similar to the time constant for oxygen recombination and therefore pressure changes due to different mechanisms are difficult to estimate. The self-discharge rate of the cell with metal hydride is two times lower in comparison to the cell with gaseous hydrogen storage alone and is a result of the lower pressure in the cell when the metal hydride is used. PMID:22711974

  20. Hydrogen absorption-desorption at metal surfaces

    International Nuclear Information System (INIS)

    Ward, C.A.; Pataki, L.

    1991-04-01

    On the basis of experimental studies, it has been proposed that when zirconium oxide (ZrO 2 ) is exposed to hydrogen at 300 degrees C or higher, a reaction occurs to produce metallic zirconium and water, thereby increasing the electrical conductivity of the oxide film and its permeability to hydrogen. A series of experiments has been performed in which specimens of zirconium and zirconium-2.5% niobium were either hydrided or deuterided in a furnace at a temperature between 300 degrees C and 800 degrees C and in an atmosphere that consisted primarily of either hydrogen (H 2 ) or deuterium (D 2 ). After cooling a specimen to room temperature, it was placed in a thermogravimetric analyzer that was equipped with a mass spectrometer, TGA-MS. Each specimen was then heated to 1200 degrees C at a controlled rate in a primarily helium atmosphere monitored with the mass spectrometer. Light water (H 2 O) evolved from the hydrided specimens and heavy water (D 2 0) from the deuterided ones and there was a weight loss of the specimens that accompanied the water evolution. The specimens having approximately the same amount of hydride but more oxide also evolved more H 2 O, and that the H 2 O did not come from reactions between impurity H 2 and oxygen (O 2 ) in the TGA-MS. Heating a zirconium or zirconium alloy specimen that contains a hydride or deuteride phase within and an oxide layer on its surface causes the hydrogen to diffuse toward the surface and when it encounters the oxide a reaction follows that produces water. The conventional mechanism for the dissipation of the imperviousness of ZrO 2 to H 2 that results from the oxide being exposed to a reducing atmosphere will not explain the water production observed in these experiments. However, the existence of the proposed reaction can account for the elevated hydrogen concentration in an oxide film that has been observed to accompany the aqueous corrosion of zirconium and the effects on both the electrical conductivity and

  1. Photoionization microscopy of hydrogen atom near a metal surface

    International Nuclear Information System (INIS)

    Yang Hai-Feng; Wang Lei; Liu Xiao-Jun; Liu Hong-Ping

    2011-01-01

    We have studied the ionization of Rydberg hydrogen atom near a metal surface with a semiclassical analysis of photoionization microscopy. Interference patterns of the electron radial distribution are calculated at different scaled energies above the classical saddle point and at various atom—surface distances. We find that different types of trajectories contribute predominantly to different manifolds in a certain interference pattern. As the scaled energy increases, the structure of the interference pattern evolves smoothly and more types of trajectories emerge. As the atom approaches the metal surface closer, there are more types of trajectories contributing to the interference pattern as well. When the Rydberg atom comes very close to the metal surface or the scaled energy approaches the zero field ionization energy, the potential induced by the metal surface will make atomic system chaotic. The results also show that atoms near a metal surface exhibit similar properties like the atoms in the parallel electric and magnetic fields. (atomic and molecular physics)

  2. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-06-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g-1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  3. Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

    Science.gov (United States)

    Bates, Michael

    Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline

  4. Removal of heavy metal from industrial wastewater using hydrogen ...

    African Journals Online (AJOL)

    The batch removal of heavy metals lead (Pb), zinc (Zn) and copper (Cu) from industrial wastewater effluent under different experimental conditions using hydrogen peroxide was investigated. Experimental results indicated that at pH 6.5, pre-treatment analysis gave the following values: Pb 57.63 mg/l, Zn 18.9 mg/l and Cu ...

  5. Hydrogen energy technology development conference. From production of hydrogen to application of utilization technologies and metal hydrides, and examples; Suiso energy gijutsu kaihatsu kaigi. Suiso no seizo kara riyo gijutsu kinzoku suisokabutsu no oyo to jirei

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1984-02-14

    The hydrogen energy technology development conference was held on February 14 to 17, 1984 in Tokyo. For hydrogen energy systems and production of hydrogen from water, 6 papers were presented for, e.g., the future of hydrogen energy, current state and future of hydrogen production processes, and current state of thermochemical hydrogen technology development. For hydrogen production, 6 papers were presented for, e.g., production of hydrogen from steel mill gas, coal and methanol. For metal hydrides and their applications, 6 papers were presented for, e.g., current state of development of hydrogen-occluding alloy materials, analysis of heat transfer in metal hydride layers modified with an organic compound and its simulation, and development of a large-size hydrogen storage system for industrial purposes. For hydrogen utilization technologies, 8 papers were presented for, e.g., combustion technologies, engines incorporating metal hydrides, safety of metal hydrides, hydrogen embrittlement of system materials, development trends of phosphate type fuel cells, and alkali and other low-temperature type fuel cells. (NEDO)

  6. A neutronic method to determine low hydrogen concentrations in metals

    International Nuclear Information System (INIS)

    Bennun, Leonardo; Santisteban, Javier; Diaz-Valdes, J.; Granada, J.R.; Mayer, R.E.

    2007-01-01

    We propose a method for the non-destructive determination of low hydrogen content in metals. The method is based on measurements of neutron inelastic scattering combined with cadmium filters. Determination is simple and the method would allow to construct a mobile device, to perform the analysis 'in situ'. We give a brief description of the usual methods to determine low hydrogen contents in solids, paying special attention to those methods supported by neutron techniques. We describe the proposed method, calculations to achieve a better sensitivity, and experimental results

  7. The influence of hydrogen on the fatigue life of metallic leaf spring components in a vacuum environment

    NARCIS (Netherlands)

    Kouters, M.H.M.; Slot, H.M.; Zwieten, W. van; Veer, J. van der

    2014-01-01

    Hydrogen is used as a process gas in vacuum environments for semiconductor manufacturing equipment. If hydrogen dissolves in metallic components during operation it can result in hydrogen embrittlement. In order to assess if hydrogen embrittlement occurs in such a vacuum environment a special

  8. Hydrogen depth resolution in multilayer metal structures, comparison of elastic recoil detection and resonant nuclear reaction method

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S. E-mail: leszekw@optushome.com.au; Grambole, D.; Kreissig, U.; Groetzschel, R.; Harding, G.; Szilagyi, E

    2002-05-01

    Four different metals: Al, Cu, Ag and Au have been used to produce four special multilayer samples to study the depth resolution of hydrogen. The layer structure of each sample was analysed using 2 MeV He Rutherford backscattering spectrometry, 4.5 MeV He elastic recoil detection (ERD) and 30 MeV F{sup 6+} HIERD. Moreover the hydrogen distribution was analysed in all samples using H({sup 15}N, {alpha}{gamma}){sup 12}C nuclear reaction analysis (NRA) with resonance at 6.385 MeV. The results show that the best depth resolution and sensitivity for hydrogen detection are offered by resonance NRA. The He ERD shows good depth resolution only for the near surface hydrogen. In this technique the depth resolution is rapidly reduced with depth due to multiple scattering effects. The 30 MeV F{sup 6+} HIERD demonstrated similar hydrogen depth resolution to He ERD for low mass metals and HIERD resolution is substantially better for heavy metals and deep layers.

  9. Study on Doppler coefficient for metallic fuel fast reactor added hydrogeneous moderator

    Energy Technology Data Exchange (ETDEWEB)

    Hirakawa, Naohiro; Iwasaki, Tomohiko; Tsujimoto, Kazuhumi [Tohoku Univ., Sendai (Japan). Faculty of Engineering; Osugi, Toshitaka; Okajima, Shigeaki; Andoh, Masaki; Nemoto, Tatsuo; Mukaiyama, Takehiko

    1998-01-01

    A series of mock-up experiments for moderator added metallic fast reactor core was carried out at FCA to obtain the experimental verification for improvement of reactivity coefficients. Softened neutron spectrum increases Doppler effect by a factor of 2, and flatter adjoint neutron spectrum decreases Na void effect by a factor of 0.6 when hydrogen to heavy metal atomic number ratio is increased from 0.02 to 0.13. The experimental results are analyzed with SLALOM and CITATION-FBR, which is the standard design code system for a fast reactor at JAERI, and SRAC95 and CITATION-FBR. The present code system gives generally good agreement with the experimental results, especially by the use of the latter, the dependence of the Doppler effect to the hydrogen to fuel element atomic number density ratio is disappeared. Therefore, it looks possible to use the present code system for the conceptual design of a fast reactor system with hydrogeneous materials. (author)

  10. Controlled delamination of metal films by hydrogen loading

    Energy Technology Data Exchange (ETDEWEB)

    Nikitin, Eugen

    2008-11-18

    n this work we quantitatively determine the adhesion energy between metal films and their substrates. Therefore a new controlled buckling technique is established, applying the strong compressive in-plane stress that results in thin films clamped on rigid substrates during hydrogen loading. When the elastic energy stored in the H-loaded thin film exceeds the adhesion energy between film and substrate, delamination occurs. At the onset of delamination, a critical hydrogen concentration, a critical stress value and a critical bending of the substrate are present, which are quantitative measures for the adhesion energy and permit its calculation. As the critical values are determined at the onset of delamination, plastic deformation is negligible, which denies the quantitative determination of adhesion energies in conventional test setups. In multilayer-systems, adhesion energies between substrates and films that hardly absorb hydrogen can be measured by the controlled buckling technique, when the films of interest are coated with hydrogen absorbing films (active layer). The measurements are performed easily and can be repeated under the same test conditions, while variables such as the thickness of the coating materials or the boundary surface structure can be varied and optimized. In this work the adhesion energies of different materials on polycarbonate and niobium on sapphire are investigated. (orig.)

  11. Enhanced hydrogen storage properties of MgH2 co-catalyzed with K2NiF6 and CNTs.

    Science.gov (United States)

    Sulaiman, N N; Ismail, M

    2016-12-06

    The composite of MgH 2 /K 2 NiF 6 /carbon nanotubes (CNTs) is prepared by ball milling, and its hydrogenation properties are studied for the first time. MgH 2 co-catalyzed with K 2 NiF 6 and CNTs exhibited an improvement in the onset dehydrogenation temperature and isothermal de/rehydrogenation kinetics compared with the MgH 2 -K 2 NiF 6 composite. The onset dehydrogenation temperature of MgH 2 doped with 10 wt% K 2 NiF 6 and 5 wt% CNTs is 245 °C, which demonstrated a reduction of 25 °C compared with the MgH 2 + 10 wt% K 2 NiF 6 composite. In terms of rehydrogenation kinetics, MgH 2 doped with 10 wt% K 2 NiF 6 and 5 wt% CNTs samples absorbed 3.4 wt% of hydrogen in 1 min at 320 °C, whereas the MgH 2 + 10 wt% K 2 NiF 6 sample absorbed 2.6 wt% of hydrogen under the same conditions. For dehydrogenation kinetics at 320 °C, the MgH 2 + 10 wt% K 2 NiF 6 + 5 wt% CNTs sample released 3.3 wt% hydrogen after 5 min of dehydrogenation. By contrast, MgH 2 doped with 10 wt% K 2 NiF 6 released 3.0 wt% hydrogen in the same time period. The apparent activation energy, E a , for the dehydrogenation of MgH 2 doped with 10 wt% K 2 NiF 6 reduced from 100.0 kJ mol -1 to 70.0 kJ mol -1 after MgH 2 was co-doped with 10 wt% K 2 NiF 6 and 5 wt% CNTs. Based on the experimental results, the hydrogen storage properties of the MgH 2 /K 2 NiF 6 /CNTs composite is enhanced because of the catalytic effects of the active species of KF, KH and Mg 2 Ni that are formed in situ during dehydrogenation, as well as the unique structure of CNTs.

  12. Tritiated hydrogen conversion on heated metallic surfaces

    International Nuclear Information System (INIS)

    Ionita, G.; Mihaila, V.; Purghel, L.; Rebigan, F.

    1995-01-01

    This work reports investigations on tritiated hydrogen conversion to tritiated water on heated metallic surfaces. The HT conversion process has been revealed for copper, aluminium and stainless steel W4541 surfaces in the temperature range 150 to 300 o C, in case of the static regime and in the range 250 to 400 o C for the dynamic case. The most significant catalytic activity was shown by the copper sample. Studies on this subject are used as input information for different nuclear accident scenarios implying tritium leakage

  13. Problems of hydrogen - water vapor - inert gas mixture use in heavy liquid metal coolant technology

    International Nuclear Information System (INIS)

    Ul'yanov, V.V.; Martynov, P.N.; Gulevskij, V.A.; Teplyakov, Yu.A.; Fomin, A.S.

    2014-01-01

    The reasons of slag deposit formation in circulation circuits with heavy liquid metal coolants, which can cause reactor core blockage, are considered. To prevent formation of deposits hydrogen purification of coolant and surfaces of circulation circuit is used. It consists in introduction of gaseous mixtures hydrogen - water vapor - rare gas (argon or helium) directly into coolant flow. The principle scheme of hydrogen purification and the processes occurring during it are under consideration. Measures which make it completely impossible to overlap of the flow cross section of reactor core, steam generators, pumps and other equipment by lead oxides in reactor facilities with heavy liquid metal coolants are listed [ru

  14. Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

    International Nuclear Information System (INIS)

    Gao Yi; Zeng, X C

    2007-01-01

    We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

  15. In-situ hydrogen in metal determination using a minimum neutron source strength and exposure time.

    Science.gov (United States)

    Hatem, M; Agamy, S; Khalil, M Y

    2013-08-01

    Water is frequently present in the environment and is a source of hydrogen that can interact with many materials. Because of its small atomic size, a hydrogen atom can easily diffuse into a host metal, and though the metal may appear unchanged for a time, the metal will eventually abruptly lose its strength and ductility. Thus, measuring the hydrogen content in metals is important in many fields, such as in the nuclear industry, in automotive and aircraft fabrication, and particularly, in offshore oil and gas fields. It has been demonstrated that the use of nuclear methods to measure the hydrogen content in metals can achieve sensitivity levels on the order of parts per million. However, the use of nuclear methods in the field has not been conducted for two reasons. The first reason is due to exposure limitations. The second reason is due to the hi-tech instruments required for better accuracy. In this work, a new method using a low-strength portable neutron source is explored in conjunction with detectors based on plastic nuclear detection films. The following are the in-situ requirements: simplicity in setup, high reliability, minimal exposure dose, and acceptable accuracy at an acceptable cost. A computer model of the experimental setup is used to reproduce the results of a proof-of-concept experiment and to predict the sensitivity levels under optimised experimental conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals

    Energy Technology Data Exchange (ETDEWEB)

    Song, Yang; Sanyal, Udishnu; Pangotra, Dhananjai; Holladay, Jamelyn D.; Camaioni, Donald M.; Gutierrez-Tinoco, Oliver Y.; Lercher, Johannes A.

    2018-03-01

    Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and

  17. Hydrogen generation from formic acid catalyzed by a metal complex under amine-free and aqueous conditions

    KAUST Repository

    Huang, Kuo-Wei; Guan, Chao; Pan, Yupeng; Hu, Jinsong; Li, Huaifeng

    2018-01-01

    invention provides catalysts used to produce hydrogen that has a satisfactory and sufficient lifespan (measured by turnover number (TON)), that has stability in the presence of moisture, air, acid, or impurities, promote a rapid reaction rate, and remain

  18. Diffusion characteristics of specific metals at the high temperature hydrogen separation; Diffusionseigenschaften bestimmter Metalle bei der Hochtemperatur-Wasserstoffabtrennung

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, Christian

    2010-09-07

    This paper evaluates the metals palladium, nickel, niobium, tantalum, titanium and vanadium according to their ability to separate hydrogen at high temperatures. This evaluation is chiefly based on a thorough consideration of the properties of diffusion for these metals. The various known hydrogen permeabilities of the metals in a temperature range from 300 to 800 C, as well as their physical and mechanical properties will be presented consistent with the current state of technology. The theory of hydrogen diffusion in metals and the mathematical basis for the calculation of diffusion will also be shown. In the empirical section of the paper, permeability measurements are taken in a temperature range of 400 to 825 C. After measurement, the formation of the oxide coating on these membranes is examined using a light-optical microscope. The results of these examinations allow a direct comparison of the different permeabilities of the various metals within the temperature range tested, and also allow for a critical evaluation of the oxide coating formed on the membranes. The final part of the paper shows the efficiency of these metals in the context of in-situ hydrogen separation in a biomass reformer. (orig.)

  19. Electronic-structure studies of metal-hydrogen systems using photoelectron spectroscopy (PES) radiation. Final report, 1 March 1980-31 August 1982

    International Nuclear Information System (INIS)

    Weaver, J.H.

    1982-09-01

    Photoelectron spectroscopy studies of hydrogen-bearing metals and alloys have provided fundamental information concerning the electronic interactions of hydrides. Studies of surface oxidation of several hydrogen storage materials (the LaNi 5 -family) evaluated the role of surface oxidation on hydrogen uptake. Collaborative band theory studies were undertaken to support experimental studies of the metal-semiconductor transition in LaH 2 -LaH 3 and of the refractory metal mono- and submonohydrides

  20. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    Science.gov (United States)

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-04

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps.

  1. Chemo-enzymatic epoxidation of olefins by carboxylic acid esters and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Ruesch gen. Klaas, M.; Warwel, S. [Inst. for Biochemistry and Technology of Lipids, H.P. Kaufmanm-Inst., Federal Centre for Cereal, Potato and Lipid Research, Muenster (Germany)

    1998-12-31

    Ethylen and, recently, butadiene can be epoxidized directly with oxygen and for the epoxidation of propylene, the use of heterogeneous transition metals and organic peroxides (Halcon-Process) is the major player. But, beside from those notable exceptions, all other epoxidations, including large ones like the epoxidation of plant oils as PVC-stabilizers (about 200.000 t/year), are carried out with peroxy acids. Because mcpba is far to expensive for most applications, short chain peracids like peracetic acid are used. Being much less stable than mcpba and thus risky handled in large amounts and high concentrations, these peroxy acids were preferably prepared in-situ. However, conventional in-situ formation of peracids has the serious drawback, that a strong acid is necessary to catalyze peroxy acid formation from the carboxylic acid and hydrogen peroxide. The presence of a strong acid in the reaction mixture often results in decreased selectivity because of the formation of undesired by-products by opening of the oxirane ring. Therefore, we propose a new method for epoxidation based on the in-situ preparation of percarboxylic acids from carboxylic acid esters and hydrogen peroxide catalyzed by a commercial, immobilized lipase. (orig.)

  2. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Energy Technology Data Exchange (ETDEWEB)

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  3. Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

    KAUST Repository

    Date, Nandan S; Hengne, Amol Mahalingappa; Huang, Kuo-Wei; Chikate, Rajeev C.; Rode, C. V.

    2018-01-01

    Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

  4. Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

    KAUST Repository

    Date, Nandan S

    2018-03-20

    Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

  5. Hydrogen metal hydride storage with integrated catalytic recombiner for mobile application

    Energy Technology Data Exchange (ETDEWEB)

    Marinescu-Pasoi, L.; Behrens, U.; Langer, G.; Gramatte, W.; Rastogi, A.K.; Schmitt, R.E. (Battelle-Institut e.V., Frankfurt am Main (DE). Dept. of Energy Technology)

    1991-01-01

    A novel, thermodynamically efficient device is under development at Battelle in Frankfurt, by which the range of hydrogen-driven cars with a metal hydride tank might be roughly doubled. The device makes use of the properties of metal hydrides, combined with catalytic combustion. Its development is funded by the Hessian Ministry of Economic Affairs and Technology; it is to be completed by the end of 1990. High-temperature hydrides (HTH) have about three times the storage capacity of low temperature hydrides (LTH), but require relatively large amounts of heat at high temperatures to release the hydrogen. The exhaust heat from combustion-engine-driven vehicles is insufficient for this, and vehicles with electric (fuel cell) drive produce practically no exhaust heat at all. The Battelle-developed device is a combination of an HTH storage cell, an LTH storage cell and a catalyst. (author).

  6. Some aspects of hydrogen interaction with amorphous metallic materials

    International Nuclear Information System (INIS)

    Spivak, L.V.; Khonik, V.A.; Skryabina, N.E.

    1995-01-01

    For the first time is considered change of some properties of amorphous metallic materials (AMM) directly in the process of hydrogenation. A supposition is made that many found effects are consequence of accumulation and relief of internal stresses during hydrogenation, exposure or following annealing of AMM. Fe 81 B 14 Si 15 , Fe 52 Co 20 Si 15 B 13 , Fe 5 Co 70 Si 15 B 10 , Fe 5 Co 58 Ni 10 Si 11 B 16 , Co 67 Fe 4 Cr 7 Si 8 B 14 84KChSP, Ni 60 Nb 35 Ti 5 , Ni 60 Nb 40 and Pd 17,5 Cu 6 Si 16.5 AMM were investigated. 24 refs.; 4 figs

  7. Zirconium-Based metal organic framework (Zr-MOF) material with high hydrostability for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2013-09-01

    Full Text Available Material-based solutions, such as metal organic frameworks (MOFs), continue to attract increasing attention as viable options for hydrogen storage applications. MOFs are widely regarded as promising materials for hydrogen storage due to their high...

  8. A non-destructive evaluation of transverse hydrogen cracking in high strength flux-cored weld metal

    International Nuclear Information System (INIS)

    Sterjovski, Z.; Carr, D. G.; Holdstock, R.; Nolan, D.; Norrish, J.

    2007-01-01

    Transverse hydrogen cracking in high strength weld metal (WM) is a potentially serious problem in thick-sections, especially in highly restrained structures. This paper presents preliminary re suits for which transverse weld metal hydrogen cracking was purposefully generated in 40 mm thick high strength WM to study the effectiveness of various non-destructive testing methods in locating and sizing transverse cracks. Transverse WM hydrogen cracking was intentionally produced by: increasing diffusible hydrogen levels through the introduction of 2% hydrogen in CO 2 shielding gas and minimizing interpass temperature and time; increasing the cracking susceptibility of the micro structure by increasing cooling rate with a large-scale test plate and maintaining an interpass temperature below 70 deg C; increasing stress levels with the use of stiffeners and end welds; and rapid postweld cooling to a temperature lower than 100 deg C. The extent of transverse weld metal hydrogen cracking was evaluated by non-destructive testing (NDT), which included conventional ultrasonic testing, radiography, acoustic emission monitoring and magnetic particle inspection. It was established that conventional ultrasonic testing was the most effective of the NDT techniques used. Acoustic emission monitoring revealed that two different types of emissions emanated from the weld metal and that the majority of emissions occurred within the first 48 hours of welding, although there was some evidence of cracking well after this initial 48 hour period. Larger sized cracks were observed near the transverse stiffeners (and weld ends) where tensile residual stresses (both longitudinal and transverse) were thought to be highest and the micro structure was therefore more susceptible to cracking. Additionally, numerous finer cracks were located in the top third of the plate (in the thickness direction) and on both sides of the weld centre line

  9. Hydrogen and dihydrogen bonding of transition metal hydrides

    Science.gov (United States)

    Jacobsen, Heiko

    2008-04-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  10. Hydrogen and dihydrogen bonding of transition metal hydrides

    International Nuclear Information System (INIS)

    Jacobsen, Heiko

    2008-01-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions

  11. Charge transfer between hydrogen(deuterium) ions and atoms in metal vapors

    International Nuclear Information System (INIS)

    Alvarez T, I.; Cisneros G, C.

    1981-01-01

    The current state of the experiments on charge transfer between hydrogen (deuterium) ions and atoms in metal vapors are given. Emphasis is given to describing different experimental techniques. The results of calculations if available, are compared with existing experimental data. (author)

  12. Creating load for new hydrogen production

    International Nuclear Information System (INIS)

    Smith, R.

    2006-01-01

    This presentation provides an update of the activities of the Hydrogen Village. The Hydrogen Village is a public-private partnership of approximately 40 companies with the goal of advancing awareness of the environmental, economic and social benefits of hydrogen and fuel cell technologies. The intent of the hydrogen village is to create a sustainable commercial market for these technologies within the Greater Toronto Area and to help to catalyze such markets in other areas

  13. Improved synthesis and hydrogen storage of a microporous metal-organic framework material

    International Nuclear Information System (INIS)

    Cheng Shaojuan; Liu Shaobing; Zhao Qiang; Li Jinping

    2009-01-01

    A microporous metal-organic framework MOF-5 [Zn 4 O(BDC) 3 , BDC = 1,4-benzenedicarboxylic] was synthesized with and without H 2 O 2 by improved methods based on the previous studies. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption, and their hydrogen storage capacities were measured. The synthesis experiments showed that H 2 O 2 favored the growth of high quality sample, large pore volume and high specific surface area. The measurements of hydrogen storage indicated that the sample with higher specific surface area and large pore volume showed better hydrogen storage behavior than other samples. It was suggested that specific surface area and pore volume influenced the capacity of hydrogen storage for MOF-5 material.

  14. Hydrogenated Graphene Nanoflakes: Semiconductor to Half-Metal Transition and Remarkable Large Magnetism

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yungang; Wang, Zhiguo; Yang, Ping; Sun, Xin; Zu, Xiaotao; Gao, Fei

    2012-03-08

    The electronic and magnetic properties of graphene nanoflakes (GNFs) can be tuned by patterned adsorption of hydrogen. Controlling the H coverage from bare GNFs to half hydrogenated and then to fully hydrogenated GNFs, the transformation of small-gap semiconductor {yields} half-metal {yields} wide-gap semiconductor occurs, accompanied by a magnetic {yields} magnetic {yields} nonmagnetic transfer and a nonmagnetic {yields} magnetic {yields} nonmagnetic transfer for triangular and hexagonal nanoflakes, respectively. The half hydrogenated GNFs, associated with strong spin polarization around the Fermi level, exhibit the unexpected large spin moment that is scaled squarely with the size of flakes. The induced spin magnetizations of these nanoflakes align parallel and lead to a substantial collective character, enabling the half hydrogenated GNFs to be spin-filtering flakes. These hydrogenation-dependent behaviors are then used to realize an attractive approach to engineer the transport properties, which provides a new route to facilitate the design of tunable spin devices.

  15. The impact of carbon materials on the hydrogen storage properties of light metal hydrides

    NARCIS (Netherlands)

    Adelhelm, P.A.; de Jongh, P.E.

    2011-01-01

    The safe and efficient storage of hydrogen is still one of the remaining challenges towards fuel cell powered cars. Metal hydrides are a promising class of materials as they allow the storage of large amounts of hydrogen in a small volume at room temperature and low pressures. However, usually the

  16. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  17. Effect of Microstructure on Hydrogen Diffusion in Weld and API X52 Pipeline Steel Base Metals under Cathodic Protection

    Directory of Open Access Journals (Sweden)

    R. C. Souza

    2017-01-01

    Full Text Available The aim of this research was to evaluate the influence of microstructure on hydrogen permeation of weld and API X52 base metal under cathodic protection. The microstructures analyzed were of the API X52, as received, quenched, and annealed, and the welded zone. The test was performed in base metal (BM, quenched base metal (QBM, annealed base metal (ABM, and weld metal (WM. Hydrogen permeation flows were evaluated using electrochemical tests in a Devanathan cell. The potentiodynamic polarization curves were carried out to evaluate the corrosion resistance of each microstructure. All tests were carried out in synthetic soil solutions NS4 and NS4 + sodium thiosulfate at 25°C. The sodium thiosulfate was used to simulate sulfate reduction bacteria (SRB. Through polarization, assays established that the microstructure does not influence the corrosion resistance. The permeation tests showed that weld metal had lower hydrogen flow than base metal as received, quenched, and annealed.

  18. Enhancing Charge Carrier Lifetime in Metal Oxide Photoelectrodes through Mild Hydrogen Treatment

    KAUST Repository

    Jang, Ji-Wook

    2017-08-25

    Widespread application of solar water splitting for energy conversion is largely dependent on the progress in developing not only efficient but also cheap and scalable photoelectrodes. Metal oxides, which can be deposited with scalable techniques and are relatively cheap, are particularly interesting, but high efficiency is still hindered by the poor carrier transport properties (i.e., carrier mobility and lifetime). Here, a mild hydrogen treatment is introduced to bismuth vanadate (BiVO4), which is one of the most promising metal oxide photoelectrodes, as a method to overcome the carrier transport limitations. Time-resolved microwave and terahertz conductivity measurements reveal more than twofold enhancement of the carrier lifetime for the hydrogen-treated BiVO4, without significantly affecting the carrier mobility. This is in contrast to the case of tungsten-doped BiVO4, although hydrogen is also a donor type dopant in BiVO4. The enhancement in carrier lifetime is found to be caused by significant reduction of trap-assisted recombination, either via passivation or reduction of deep trap states related to vanadium antisite on bismuth or vanadium interstitials according to density functional theory calculations. Overall, these findings provide further insights on the interplay between defect modulation and carrier transport in metal oxides, which benefit the development of low-cost, highly-efficient solar energy conversion devices.

  19. Ortho-para-conversion of hydrogen in films of rare earth metals

    International Nuclear Information System (INIS)

    Zhavoronkova, K.N.; Peshkov, A.V.

    1979-01-01

    Investigated is specific catalytic activity of REE to clarify to what an extent the change of electron structure of the metals might influence their catalytic properties. Conducted is investigation of Sc, It, La and other lanthanides, except Eu amd Pm prepared in the form of metallic films, impowdered in vacuum of 10 -7 torr. It is established, that pape earth elements as catalysts of low-temperature ortho-para-conversion od hydrogen are divided into 2 groups, differing by mechanism of the reaction. Comparison of experimental results with the calculation results of absolute rates of paramagnetic conversion and also with investigation results of isotopjc exchange on these metals showed, that on the metals of group 1 conversjon proceeds according to chemical mechanism, and on the metals of group 2 - according to oscillating magnetic mechanism

  20. Cold, muon-catalyzed fusion - just another swarm experiment?

    International Nuclear Information System (INIS)

    Robson, R.E.

    1992-01-01

    The paper briefly reviewed the muon-catalyzed fusion cycle and indicated how it may be likened to a swarm experiment. In particular, it has been pointed out that an external electric field can influence the properties of a muon swarm (and reactive derivatives), just as it can for ion and electron swarms. Since n 0 is typically around liquid hydrogen densities, very large fields, E≥10 9 V/m, would be required to achieve the desired outcome. This is presently achievable in small regions of intense laser focus, but it remains to be seen whether muon-catalyzed fusion experiments can actually be influenced in this way. 20 refs., 4 figs

  1. Optimization and comprehensive characterization of metal hydride based hydrogen storage systems using in-situ Neutron Radiography

    Science.gov (United States)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Bücherl, T.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2016-10-01

    For the storage of hydrogen, complex metal hydrides are considered as highly promising with respect to capacity, reversibility and safety. The optimization of corresponding storage tanks demands a precise and time-resolved investigation of the hydrogen distribution in scaled-up metal hydride beds. In this study it is shown that in situ fission Neutron Radiography provides unique insights into the spatial distribution of hydrogen even for scaled-up compacts and therewith enables a direct study of hydrogen storage tanks. A technique is introduced for the precise quantification of both time-resolved data and a priori material distribution, allowing inter alia for an optimization of compacts manufacturing process. For the first time, several macroscopic fields are combined which elucidates the great potential of Neutron Imaging for investigations of metal hydrides by going further than solely 'imaging' the system: A combination of in-situ Neutron Radiography, IR-Thermography and thermodynamic quantities can reveal the interdependency of different driving forces for a scaled-up sodium alanate pellet by means of a multi-correlation analysis. A decisive and time-resolved, complex influence of material packing density is derived. The results of this study enable a variety of new investigation possibilities that provide essential information on the optimization of future hydrogen storage tanks.

  2. On physics of the hydrogen plasticization and embrittlement of metallic materials, relevance to the safety and standards' problems

    International Nuclear Information System (INIS)

    Yury S Nechaev; Georgy A Filippov; T Nejat Veziroglu

    2006-01-01

    In the present contribution, some related fundamental problems of revealing micro mechanisms of hydrogen plasticization, superplasticity, embrittlement, cracking, blistering and delayed fracture of some technologically important industrial metallic materials are formulated. The ways are considered of these problems' solution and optimizing the technological processes and materials, particularly in the hydrogen and gas-petroleum industries, some aircraft, aerospace and automobile systems. The results are related to the safety and standardization problems of metallic materials, and to the problem of their compatibility with hydrogen. (authors)

  3. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Börries, S., E-mail: stefan.boerries@hzg.de [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Metz, O.; Pranzas, P.K. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Bücherl, T. [ZTWB Radiochemie München (RCM), Technische Universität München (TUM), Walther-Meissner-Str. 3, D-85748 Garching (Germany); Söllradl, S. [Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRMII), Technische Universität München (TUM), Lichtenbergstr. 1, D-85748 Garching (Germany); Dornheim, M.; Klassen, T.; Schreyer, A. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany)

    2015-10-11

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

  4. Hydrogen Storage using Metal Hydrides in a Stationary Cogeneration System

    International Nuclear Information System (INIS)

    Botzung, Maxime; Chaudourne, Serge; Perret, Christian; Latroche, Michel; Percheron-Guegan, Annick; Marty Philippe

    2006-01-01

    In the frame of the development of a hydrogen production and storage unit to supply a 40 kW stationary fuel cell, a metal hydride storage tank was chosen according to its reliability and high energetic efficiency. The study of AB5 compounds led to the development of a composition adapted to the project needs. The absorption/desorption pressures of the hydride at 75 C (2 / 1.85 bar) are the most adapted to the specifications. The reversible storage capacity (0.95 %wt) has been optimized to our work conditions and chemical kinetics is fast. The design of the Combined Heat and Power CHP system requires 5 kg hydrogen storage but in a first phase, only a 0.1 kg prototype has been realised and tested. Rectangular design has been chosen to obtain good compactness with an integrated plate fin type heat exchanger designed to reach high absorption/desorption rates. In this paper, heat and mass transfer characteristics of the Metal Hydride tank (MH tank) during absorption/desorption cycles are given. (authors)

  5. Transition Metal Catalyzed Synthesis of Carboxylic Acids, Imines, and Biaryls

    DEFF Research Database (Denmark)

    Santilli, Carola; Madsen, Robert

    the carboxylate.  Manganese catalyzed radical Kumada-type reaction between aryl halidesand aryl Grignard reagents. The reaction between aryl halides and aryl Grignard reagents catalyzed by MnCl2 has been extended to several methyl-substituted aryl iodide reagents byperforming the reaction at 120 ˚C in a microwave...... oven (Scheme ii). A limitation of the heterocoupling process is the concomitant dehalogenation of the aryl halide and homocoupling of the Grignard reagent leading low to moderate yields of the desired heterocoupling product. The mechanism of the cross-coupling process was investigated by performing two...

  6. Transition-Metal-Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

    KAUST Repository

    Guo, Lin; Rueping, Magnus

    2018-01-01

    Transition metal‐catalyzed decarbonylative coupling reactions have emerged as a powerful alternative to conventional cross‐coupling protocols due to the advantages associated with the use of carbonyl‐containing functionalities as coupling electrophiles instead of commonly used organohalides or sulfates. A wide variety of novel transformations based on this concept have been successfully achieved, including decarbonylative carbon–carbon and carbon–heteroatom bond forming reactions. In this Review, we summarize the recent progress in this field and present a comprehensive overview of metal‐catalyzed decarbonylative coupling reactions with carbonyl derivatives.

  7. Transition-Metal-Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

    KAUST Repository

    Guo, Lin

    2018-05-14

    Transition metal‐catalyzed decarbonylative coupling reactions have emerged as a powerful alternative to conventional cross‐coupling protocols due to the advantages associated with the use of carbonyl‐containing functionalities as coupling electrophiles instead of commonly used organohalides or sulfates. A wide variety of novel transformations based on this concept have been successfully achieved, including decarbonylative carbon–carbon and carbon–heteroatom bond forming reactions. In this Review, we summarize the recent progress in this field and present a comprehensive overview of metal‐catalyzed decarbonylative coupling reactions with carbonyl derivatives.

  8. Hydrogen storage compositions

    Science.gov (United States)

    Li, Wen; Vajo, John J.; Cumberland, Robert W.; Liu, Ping

    2011-04-19

    Compositions for hydrogen storage and methods of making such compositions employ an alloy that exhibits reversible formation/deformation of BH.sub.4.sup.- anions. The composition includes a ternary alloy including magnesium, boron and a metal and a metal hydride. The ternary alloy and the metal hydride are present in an amount sufficient to render the composition capable of hydrogen storage. The molar ratio of the metal to magnesium and boron in the alloy is such that the alloy exhibits reversible formation/deformation of BH.sub.4.sup.- anions. The hydrogen storage composition is prepared by combining magnesium, boron and a metal to prepare a ternary alloy and combining the ternary alloy with a metal hydride to form the hydrogen storage composition.

  9. Metallic Membranes for High Temperature Hydrogen Separation

    DEFF Research Database (Denmark)

    Ma, Y.H.; Catalano, Jacopo; Guazzone, Federico

    2013-01-01

    membrane fabrication methods have matured over the last decades, and the deposition of very thin films (1–5 µm) of Pd over porous ceramics or modified porous metal supports is quite common. The H2 permeances and the selectivities achieved at 400–500 °C were in the order of 50–100 Nm3/m/h/bar0.5 and greater......Composite palladium membranes have extensively been studied in laboratories and, more recently, in small pilot industrial applications for the high temperature separation of hydrogen from reactant mixtures such as water-gas shift (WGS) reaction or methane steam reforming (MSR). Composite Pd...... than 1000, respectively. This chapter describes in detail composite Pd-based membrane preparation methods, which consist of the grading of the support and the deposition of the dense metal layer, their performances, and their applications in catalytic membrane reactors (CMRs) at high temperatures (400...

  10. Electronic specific heats in metal--hydrogen systems

    International Nuclear Information System (INIS)

    Flotow, H.E.

    1979-01-01

    The electronic specific heats of metals and metal--hydrogen systems can in many cases be evaluated from the measured specific heats at constant pressure, C/sub p/, in the temperature range 1 to 10 K. For the simplest case, C/sub p/ = γT + βT 3 , where γT represents the specific heat contribution associated with the conduction electrons, and βT 3 represents lattice specific heat contribution. The electronic specific heat coefficient, γ, is important because it is proportional to electron density of states at the Fermi surface. A short description of a low temperature calorimetric cryostat employing a 3 He/ 4 He dilution refrigeration is given. Various considerations and complications encountered in the evaluation of γ from specific heat data are discussed. Finally, the experimental values of γ for the V--Cr--H system and for the Lu--H system are summarized and the variations of γ as function of alloy composition are discussed

  11. A magnetic investigation of phase transitions for metal-hydrogen systems based on nickel by means of computer-aided data acquisition

    International Nuclear Information System (INIS)

    Martin, W.E.

    1986-01-01

    In the present thesis the magnetic behaviour of Nickel-based metal-hydrogen systems is investigated in relation to its background in metal physics, in order to get information on the formation and the decomposition of metal-hydrogen phases. The magnetic investigations are performed at the systems Ni-Cu-H and Ni-Cr-H with Cu up to 40 at% and Cr up to 7 at%. The differential susceptibility is measured during hydration and decomposition of hydrides and the connection between magnetic moment and hydrogen concentration is discussed. (BHO)

  12. Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts

    Science.gov (United States)

    Jeon, Ki-Joon; Moon, Hoi Ri; Ruminski, Anne M.; Jiang, Bin; Kisielowski, Christian; Bardhan, Rizia; Urban, Jeffrey J.

    2011-04-01

    Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg-1 ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria—absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH2 has a ΔHf˜75 kJ mol-1), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 °C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts.

  13. Hydrogen Storage Engineering Center of Excellence Metal Hydride Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2014-05-31

    The Hydrogen Storage Engineering Center of Excellence (HSECoE) was established in 2009 by the U.S. Department of Energy (DOE) to advance the development of materials-based hydrogen storage systems for hydrogen-fueled light-duty vehicles. The overall objective of the HSECoE is to develop complete, integrated system concepts that utilize reversible metal hydrides, adsorbents, and chemical hydrogen storage materials through the use of advanced engineering concepts and designs that can simultaneously meet or exceed all the DOE targets. This report describes the activities and accomplishments during Phase 1 of the reversible metal hydride portion of the HSECoE, which lasted 30 months from February 2009 to August 2011. A complete list of all the HSECoE partners can be found later in this report but for the reversible metal hydride portion of the HSECoE work the major contributing organizations to this effort were the United Technology Research Center (UTRC), General Motors (GM), Pacific Northwest National Laboratory (PNNL), the National Renewable Energy Laboratory (NREL) and the Savannah River National Laboratory (SRNL). Specific individuals from these and other institutions that supported this effort and the writing of this report are included in the list of contributors and in the acknowledgement sections of this report. The efforts of the HSECoE are organized into three phases each approximately 2 years in duration. In Phase I, comprehensive system engineering analyses and assessments were made of the three classes of storage media that included development of system level transport and thermal models of alternative conceptual storage configurations to permit detailed comparisons against the DOE performance targets for light-duty vehicles. Phase 1 tasks also included identification and technical justifications for candidate storage media and configurations that should be capable of reaching or exceeding the DOE targets. Phase 2 involved bench-level testing and

  14. Thermomechanics of hydrogen storage in metallic hydrides: modeling and analysis

    Czech Academy of Sciences Publication Activity Database

    Roubíček, Tomáš; Tomassetti, G.

    2014-01-01

    Roč. 19, č. 7 (2014), s. 2313-2333 ISSN 1531-3492 R&D Projects: GA ČR GA201/09/0917 Institutional support: RVO:61388998 Keywords : metal-hydrid phase transformation * hydrogen diffusion * swelling Subject RIV: BA - General Mathematics Impact factor: 0.768, year: 2014 http://aimsciences.org/journals/pdfs.jsp?paperID=10195&mode=full

  15. First-principles study of hydrogen dissociation and diffusion on transition metal-doped Mg(0 0 0 1) surfaces

    International Nuclear Information System (INIS)

    Wang, Zhiwen; Guo, Xinjun; Wu, Mingyi; Sun, Qiang; Jia, Yu

    2014-01-01

    First-principles calculations within the density functional theory (DFT) have been carried out to study hydrogen molecules dissociation and diffusion on clean and transition metals (TMs) doped Mg(0 0 0 1) surfaces following Pozzo et al. work. Firstly, the stability of Mg(0 0 0 1) surface doped with transition metals atom has been studied. The results showed that transition metals on the left of the table tend to substitute Mg in the second layer, while the other transition metals prefer to substitute Mg in the first layer. Secondly, we studied hydrogen molecules dissociation and diffusion on clean and Mg(0 0 0 1) surfaces which the transition metal atoms substituted both in the first layer and second layer. When transition metal atoms substitute in the first layer, the results agree with the Pozzo et al. result; when transition metal atoms substitute in the second layer, the results showed that the transition metals on the left of the periodic table impact on the dissociation barriers is less. However, for the transition metals (Mn, Fe, Co, Ni) on the right, there is a great impact on the barriers. The transition metals doped surfaces bind the dissociated H atoms loosely, making them easily diffused. The results further reveal that the Fe dopant on the Mg surface is the best choice for H 2 dissociation and hydrogen storage.

  16. The effect of a micro bubble dispersed gas phase on hydrogen isotope transport in liquid metals under nuclear irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Fradera, J., E-mail: jfradera@ubu.es; Cuesta-López, S., E-mail: scuesta@ubu.es

    2013-12-15

    The present work intend to be a first step towards the understanding and quantification of the hydrogen isotope complex phenomena in liquid metals for nuclear technology. Liquid metals under nuclear irradiation in, e.g., breeding blankets of a nuclear fusion reactor would generate tritium which is to be extracted and recirculated as fuel. At the same time that tritium is bred, helium is also generated and may precipitate in the form of nano bubbles. Other liquid metal systems of a nuclear reactor involve hydrogen isotope absorption processes, e.g., tritium extraction system. Hence, hydrogen isotope absorption into gas bubbles modelling and control may have a capital importance regarding design, operation and safety. Here general models for hydrogen isotopes transport in liquid metal and absorption into gas phase, that do not depend on the mass transfer limiting regime, are exposed and implemented in OpenFOAM® CFD tool for 0D–3D simulations. Results for a 0D case show the impact of a He dispersed phase of nano bubbles on hydrogen isotopes inventory at different temperatures as well as the inventory evolution during a He nucleation event. In addition, 1D and 2D axisymmetric cases are exposed showing the effect of a He dispersed gas phase on hydrogen isotope permeation through a lithium lead eutectic alloy and the effect of vortical structures on hydrogen isotope transport at a backward facing step. Exposed results give a valuable insight on current nuclear technology regarding the importance of controlling hydrogen isotope transport and its interactions with nucleation event through gas absorption processes.

  17. Impact of heavy metals on hydrogen production from organic fraction of municipal solid waste using co-culture of Enterobacter aerogenes and E. Coli.

    Science.gov (United States)

    Sharma, Preeti; Melkania, Uma

    2018-05-01

    In the present study, the effect of heavy metals (lead, mercury, copper, and chromium) on the hydrogen production from the organic fraction of municipal solid waste (OFMSW) was investigated using co-culture of facultative anaerobes Enterobacter aerogenes and E. coli. Heavy metals were applied at concentration range of 0.5, 1, 2, 5, 10, 20, 50 and 100 mg/L. The results revealed that lead, mercury, and chromium negatively affected hydrogen production for the range of concentrations applied. Application of copper slightly enhanced hydrogen production at low concentration and resulted in the hydrogen yield of 36.0 mLH 2 /gCarbo initial with 10 mg/L copper supplementation as compared to 24.2 mLH 2 /gCarbo initial in control. However, the higher concentration of copper (>10 mg/L) declined hydrogen production. Hydrogen production inhibition potential of heavy metals can be arranged in the following increasing order: Cu 2+  metal addition. Thus, the present study reveals that the presence of heavy metals in the feedstock is detrimental for the hydrogen production. Therefore, it is essential to remove the toxic heavy metals prior to anaerobic digestion. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Hydrogen and dihydrogen bonding of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

    2008-04-03

    Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  19. Role of synergism effect of mixed metal oxides on molecular hydrogen formation from photocatalitic water splitting

    International Nuclear Information System (INIS)

    Mahmudov, H.M.; Ismayilova, M.K.; Jafarova, N.A.; Azizova, K.V.

    2017-01-01

    The paper deals with hydrogen production using photocatalysis. In particular, we focus on the role of synergism on the reaction rate. For hydrogen production presented photocatalyst is composed of nanoAl_2O_3 and dispers TiO_2. Yet, the presence of the two mixed metal oxides together results in considerable enhancement of the reaction rate. The main reason for this is the increase of the charge carriers lifetime allowing for electron transfer to hydrogen ions and hole transfer to oxygen ions. It was investigated the mechanism of water splitting in presence of mixed nanocatalysed. It has been shown that the effect occurs during irradiation as a result of photooxidation of water with mixed metal oxides catalyst.

  20. Hydrogen production and metal-dye bioremoval by a Nostoc linckia strain isolated from textile mill oxidation pond.

    Science.gov (United States)

    Mona, Sharma; Kaushik, Anubha; Kaushik, C P

    2011-02-01

    Biohydrogen production by Nostoc linckia HA-46, isolated from a textile-industry oxidation-pond was studied by varying light/dark period, pH, temperature and ratio of carbon-dioxide and argon in the gas-mixture. Hydrogen production rates were maximum under 18 h of light and 6 h of darkness, pH 8.0, 31°C, a CO(2):Ar ratio 2:10. Hydrogen production of the strain acclimatized to 20 mg/L of chromium/cobalt and 100 mg/L of Reactive red 198/crystal violet dye studied in N-supplemented/deficient medium was 6-10% higher in the presence of 1.5 g/L of NaNO(3). Rates of hydrogen production in the presence of dyes/metals by the strain (93-105 μmol/h/mg Chlorophyll) were significantly higher than in medium without metals/dyes serving as control (91.3 μmol/h/mg Chlorophyll). About 58-60% of the two metals and 35-73% of dyes were removed by cyanobacterium. Optimal conditions of temperature, pH and metals/dyes concentration for achieving high hydrogen production and wastewater treatment were found practically applicable as similar conditions are found in the effluent of regional textile-mills. Copyright © 2010 Elsevier Ltd. All rights reserved.

  1. Hydrogen adsorption on metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs)

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, E.; Chahine, R.; Benard, P.; Lafi, L.; Dorval-Douville, G.; Chandonia, P.-A. [Univ. du Quebec a Trois-Rivieres, Inst. de recherche sur l' hydrogene, Trois-Rivieres, Quebec (Canada)]. E-mail: Lyubov.Lafi@uqtr.ca

    2006-07-01

    'Full text:' In recent years, several novel carbon-based microporous materials such as single-walled carbon nanotubes (SWNTs) and metal-organic frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. Hydrogen adsorption measurements on Al-, Cr- and Zn-based metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs) are presented. The measurements were performed at temperatures ranging from 77 to 300K and pressures up to 50 atm using a volumetric approach. The maximum excess adsorption at 77K ranges from 2,8 to 3,9 wt % for the MOFs and from 1,5 to 2,5 wt % for the SWNTs. These values are reached at pressures below 40 atm. At room temperature and 40 atm, modest amounts of hydrogen are adsorbed (< 0,4 wt %). A Dubinin-Astakhov (DA) approach is used to investigate the measured adsorption isotherms and retrieve energetic and structural parameters. The adsorption enthalpy averaged over filling is found to be about 2,9 kJ/mol for the MOF-5 and about 3,6 - 4,2 kJ/mol for SWNTs. The uptake of hydrogen on SWNTs and MOF-5 appears to be due to physisorption and can be described, through the DA-model, by a traditional theory of micropore filling. (author)

  2. Research on the surface chemical behavior of uranium metal in hydrogen atmosphere by XPS

    International Nuclear Information System (INIS)

    Fu Xiaoguo; Wang Xiaolin; Yu Yong; Zhao Zhengping

    2001-01-01

    The surface chemical behavior clean uranium metal in hydrogen atmosphere at 100 and 200 degree C is studied by X-ray photoelectron spectroscopy (XPS), respectively. It leads to hydriding reaction when the hydrogen exposure is 12.0 Pa·s, and the U4f 7/2 binding energy of UH 3 is found to be 378.7 eV. The higher temperature (200 degree C) is beneficial to UH 3 formation at the same hydrogen exposures. XPS elemental depth profiles indicate that the distribution of uranium surface layer is UO 2 , UH 3 and U after exposure to 174.2 Pa·s hydrogen

  3. Hydrogenation of cyclohexene with LaNi5−xAlxHn metal hydrides suspended in cyclohexane or ethanol

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, W.P.M. van

    1993-01-01

    The hydrogenation of cyclohexene on the metal hydride forming alloys LaNi4.8Al0.2, LaNi4.9Al0.1 and LaNi5, all suspended in cyclohexane and LaNi5 suspended in ethanol, has been investigated. Two sources for hydrogen are recognized: hydrogen supplied by the gas phase and hydrogen which is available

  4. Hydrogenation of cyclohexene with LaNi@#5@#-@#x@#Al@#x@#Hn metal hydrides, suspended in cyclohexane or ethanol

    NARCIS (Netherlands)

    Snijder, E.D.; Snijder, E.D.; Versteeg, Geert; van Swaaij, Willibrordus Petrus Maria

    1993-01-01

    The hydrogenation of cyclohexene on the metal hydride forming alloys LaNi4.8Al0.2, LaNi4.9Al0.1 and LaNi5, all suspended in cyclohexane and LaNi5 suspended in ethanol, has been investigated. Two sources for hydrogen are recognized: hydrogen supplied by the gas phase and hydrogen which is available

  5. Computational investigation of the effects of barrier layers on the permeation of hydrogen through metals

    International Nuclear Information System (INIS)

    Perkins, W.G.

    1975-01-01

    Results of a computational investigation of the permeation behavior of oxide-coated metal membranes are presented. A steady-state permeation model was developed which promises to be useful in evaluation of oxide layers on metals as hydrogen permeation barriers. The pressure and thickness dependence of steady state permeation through oxide-coated metal membranes is described using plots of logarithmic functions. (U.S.)

  6. An efficient and high-yielding one-pot synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-diones catalyzed by sodium hydrogen carbonate under solvent-free conditions

    OpenAIRE

    Asieh Vafaee; Abolghasem Davoodnia; Mehdi Pordel; Mohammad Reza Bozorgmehr

    2015-01-01

    Sodium hydrogen carbonate, NaHCO3, efficiently catalyzes the one-pot, three-component reaction of phthalhydrazide, an aromatic aldehyde, and malononitrile or ethyl cyanoacetate under solvent-free conditions, to afford the corresponding 1H-pyrazolo[1,2-b]phthalazine-5,10-diones in high yields. Easy work‐up, inexpensive and readily available catalyst and avoiding the use of harmful organic solvents are other advantages of this simple procedure.

  7. Ultrahigh figure-of-merit for hydrogen generation from sodium borohydride using ternary metal catalysts

    Science.gov (United States)

    Hu, Lunghao; Ceccato, R.; Raj, R.

    We report further increase in the figure-of-merit (FOM) for hydrogen generation from NaBH 4 than reported in an earlier paper [1], where a sub-nanometer layer of metal catalysts are deposited on carbon nanotube paper (CNT paper) that has been functionalized with polymer-derived silicon carbonitride (SiCN) ceramic film. Ternary, Ru-Pd-Pt, instead of the binary Pd-Pt catalyst used earlier, together with a thinner CNT paper is shown to increase the figure-of-merit by up to a factor of six, putting is above any other known catalyst for hydrogen generation from NaBH 4. The catalysts are prepared by first impregnating the functionalized CNT-paper with solutions of the metal salts, followed by reduction in a sodium borohydride solution. The reaction mechanism and the catalyst efficiency are described in terms of an electric charge transfer, whereby the negative charge on the BH 4 - ion is exchanged with hydrogen via the electronically conducting SiCN/CNT substrate [1].

  8. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

    International Nuclear Information System (INIS)

    Yan, Kai; Chen, Aicheng

    2013-01-01

    Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

  9. Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

    DEFF Research Database (Denmark)

    Ghalehshahi, Hajar Golshadi; Madsen, Robert

    2017-01-01

    A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...... into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver...

  10. Hydrogen-absorbing alloys for the nickel-metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Mingming Geng; Jianwen Han; Feng Feng [University of Windsor, Ontario (Canada). Mechanical and Materials Engineering; Northwood, D.O. [University of Windsor, Ontario (Canada). Mechanical and Materials Engineering]|[Ryerson Polytechnic University, Toronto (Canada)

    1998-12-31

    In recent years, owing to the rapid development of portable electronic and electrical appliances, the market for rechargeable batteries has increased at a high rate. The nickel-metal hydride battery (Ni/MH) is one of the more promising types, because of its high capacity, high-rate charge/discharge capability and non-polluting nature. This type of battery uses a hydrogen storage alloy as its negative electrode. The characteristics of the Ni/MH battery, including discharge voltage, high-rate discharge capability and charge/discharge cycle lifetime are mainly determined by the construction of the negative electrode and the composition of the hydrogen-absorbing alloy. The negative electrode of the Ni/MH battery described in this paper was made from a mixture of hydrogen-absorbing alloy, nickel powder and polytetrafluoroethylene (PTFE). A multicomponent MmNi{sub 5}-based alloy (Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85} Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35}) was used as the hydrogen-absorbing alloy. The discharge characteristics of the negative electrode, including discharge capacity, cycle lifetime, and polarization overpotential, were studied by means of electrochemical experiments and analysis. The decay of the discharge capacity for the Ni/MH battery (AA size, 1 Ah) was about 1% after 100 charge/discharge cycles and 10% after 500 charge/discharge cycles. (author)

  11. Graphene–Noble Metal Nano-Composites and Applications for Hydrogen Sensors

    Directory of Open Access Journals (Sweden)

    Sukumar Basu

    2017-10-01

    Full Text Available Graphene based nano-composites are relatively new materials with excellent mechanical, electrical, electronic and chemical properties for applications in the fields of electrical and electronic devices, mechanical appliances and chemical gadgets. For all these applications, the structural features associated with chemical bonding that involve other components at the interface need in-depth investigation. Metals, polymers, inorganic fibers and other components improve the properties of graphene when they form a kind of composite structure in the nano-dimensions. Intensive investigations have been carried out globally in this area of research and development. In this article, some salient features of graphene–noble metal interactions and composite formation which improve hydrogen gas sensing properties—like higher and fast response, quick recovery, cross sensitivity, repeatability and long term stability of the sensor devices—are presented. Mostly noble metals are effective for enhancing the sensing performance of the graphene–metal hybrid sensors, due to their superior catalytic activities. The experimental evidence for atomic bonding between metal nano-structures and graphene has been reported in the literature and it is theoretically verified by density functional theory (DFT. Multilayer graphene influences gas sensing performance via intercalation of metal and non-metal atoms through atomic bonding.

  12. Investigation of hydrogen micro-kinetics in metals with ion beam implantation and analysis

    International Nuclear Information System (INIS)

    Wang, T.S.; Peng, H.B.; Lv, H.Y.; Han, Y.C.; Grambole, D.; Herrmann, F.

    2007-01-01

    One of the most important subjects in the fusion material research is to study the hydrogen and helium concentration, diffusion and evolution in the structure material of fusion reactor, since the hydrogen and helium can be continuously produced by the large dose fast neutron irradiation on material. Various analysis Methods can be used, but the ion beam analysis method has some advantages for studying the hydrogen behaviors in nano- or micrometer resolution. In this work, the hydrogen motion and three-dimensional distribution after implantation into metal has been studied by resonance NRA, micro-ERDA and XRD etc Methods. The resolution of the H-depth-profile is in nanometer level and the lateral resolution can be reached to 2 micrometers. The evolution of hydrogen depth-profile in a titanium sample has been studied versus the change of normal stress in samples. Evident hydrogen diffusion has been observed, while a normal stress is changed in the range of 107-963 MPa. A new phase transformation during the hydrogenation is observed by the in-situ XRD analysis. The further study on the hydrogen behaviors in the structure materials of fusion reactor is in plan. (authors)

  13. Mechanical tunability via hydrogen bonding in metal-organic frameworks with the perovskite architecture.

    Science.gov (United States)

    Li, Wei; Thirumurugan, A; Barton, Phillip T; Lin, Zheshuai; Henke, Sebastian; Yeung, Hamish H-M; Wharmby, Michael T; Bithell, Erica G; Howard, Christopher J; Cheetham, Anthony K

    2014-06-04

    Two analogous metal-organic frameworks (MOFs) with the perovskite architecture, [C(NH2)3][Mn(HCOO)3] (1) and [(CH2)3NH2][Mn(HCOO)3] (2), exhibit significantly different mechanical properties. The marked difference is attributed to their distinct modes of hydrogen bonding between the A-site amine cation and the anionic framework. The stronger cross-linking hydrogen bonding in 1 gives rise to Young's moduli and hardnesses that are up to twice those in 2, while the thermal expansion is substantially smaller. This study presents clear evidence that the mechanical properties of MOF materials can be substantially tuned via hydrogen-bonding interactions.

  14. Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory

    DEFF Research Database (Denmark)

    Valdes, Alvaro; Brillet, Jeremie; Graetzel, Michael

    2012-01-01

    An overview of a collaborative experimental and theoretical effort toward efficient hydrogen production via photoelectrochemical splitting of water into di-hydrogen and di-oxygen is presented here. We present state-of-the-art experimental studies using hematite and TiO2 functionalized with gold n...... nanoparticles as photoanode materials, and theoretical studies on electro and photo-catalysis of water on a range of metal oxide semiconductor materials, including recently developed implementation of self-interaction corrected energy functionals....

  15. Improved Hydrogen Gas Getters for TRU Waste -- Final Report

    International Nuclear Information System (INIS)

    Mark Stone; Michael Benson; Christopher Orme; Thomas Luther; Eric Peterson

    2005-01-01

    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

  16. 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

  17. Mesoscopic quantum effects in a bad metal, hydrogen-doped vanadium dioxide

    Science.gov (United States)

    Hardy, Will J.; Ji, Heng; Paik, Hanjong; Schlom, Darrell G.; Natelson, Douglas

    2017-05-01

    The standard treatment of quantum corrections to semiclassical electronic conduction assumes that charge carriers propagate many wavelengths between scattering events, and succeeds in explaining multiple phenomena (weak localization magnetoresistance (WLMR), universal conductance fluctuations, Aharonov-Bohm oscillations) observed in polycrystalline metals and doped semiconductors in various dimensionalities. We report apparent WLMR and conductance fluctuations in H x VO2, a poor metal (in violation of the Mott-Ioffe-Regel limit) stabilized by the suppression of the VO2 metal-insulator transition through atomic hydrogen doping. Epitaxial thin films, single-crystal nanobeams, and nanosheets show similar phenomenology, though the details of the apparent WLMR seem to depend on the combined effects of the strain environment and presumed doping level. Self-consistent quantitative analysis of the WLMR is challenging given this and the high resistivity of the material, since the quantitative expressions for WLMR are derived assuming good metallicity. These observations raise the issue of how to assess and analyze mesoscopic quantum effects in poor metals.

  18. Electronic Structure Calculations of Hydrogen Storage in Lithium-Decorated Metal-Graphyne Framework.

    Science.gov (United States)

    Kumar, Sandeep; Dhilip Kumar, Thogluva Janardhanan

    2017-08-30

    Porous metal-graphyne framework (MGF) made up of graphyne linker decorated with lithium has been investigated for hydrogen storage. Applying density functional theory spin-polarized generalized gradient approximation with the Perdew-Burke-Ernzerhof functional containing Grimme's diffusion parameter with double numeric polarization basis set, the structural stability, and physicochemical properties have been analyzed. Each linker binds two Li atoms over the surface of the graphyne linker forming MGF-Li 8 by Dewar coordination. On saturation with hydrogen, each Li atom physisorbs three H 2 molecules resulting in MGF-Li 8 -H 24 . H 2 and Li interact by charge polarization mechanism leading to elongation in average H-H bond length indicating physisorption. Sorption energy decreases gradually from ≈0.4 to 0.20 eV on H 2 loading. Molecular dynamics simulations and computed sorption energy range indicate the high reversibility of H 2 in the MGF-Li 8 framework with the hydrogen storage capacity of 6.4 wt %. The calculated thermodynamic practical hydrogen storage at room temperature makes the Li-decorated MGF system a promising hydrogen storage material.

  19. Chitosan catalyzes hydrogen evolution at mercury electrodes

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil; Římánková, Ludmila

    2014-01-01

    Roč. 44, JUL2014 (2014), s. 59-62 ISSN 1388-2481 R&D Projects: GA ČR(CZ) GAP301/11/2055 Institutional support: RVO:68081707 Keywords : Chitosan * Glucosamine-containing polymers * Catalytic hydrogen evolution Subject RIV: BO - Biophysics Impact factor: 4.847, year: 2014

  20. Ni-polymer nanogel hybrid particles: A new strategy for hydrogen production from the hydrolysis of dimethylamine-borane and sodium borohydride

    International Nuclear Information System (INIS)

    Cai, Haokun; Liu, Liping; Chen, Qiang; Lu, Ping; Dong, Jian

    2016-01-01

    Efficient non-precious metal catalysts are crucial for hydrogen production from borohydride compounds in aqueous media via hydrogen atoms in water. A method for preparing magnetic polymer nanoparticles is developed in this study based on the chemical deposition of nickel onto hydrophilic polymer nanogels. High-resolution transmission electron microscopic and XPS analyses show that Ni exists mainly in the form of NiO in nanogels. Excellent catalytic activities of the nanoparticles are demonstrated for hydrogen generation from the hydrolysis of dimethylamine-borane and sodium borohydride in which the initial TOF (turn-over frequencies) are 376 and 1919 h"−"1, respectively. Kinetic studies also reveal an Arrhenius activation energy of 50.96 kJ mol"−"1 for the hydrolysis of dimethylamine-borane and 47.82 kJ mol"−"1 for the hydrolysis of sodium borohydride, which are lower than those catalyzed by Ru metal. Excellent reusability and the use of water for hydrogen production from dimethylamine-borane provide the additional benefit of using a hybrid catalyst. The principle illustrated in the present study offers a new strategy to explore polymer-transition metal hybrid particles for hydrogen energy technology. - Highlights: • Electroless Ni plating on polymer nanogels generated recyclable catalysts. • The Ni particles proved efficient for H_2 production from borohydride compounds. • The catalysts have lower activation energies than Ru for the hydrolysis. • Borohydride hydrolysis is more beneficial than dehydrogenation in organic solvent.

  1. A Novel Synthesis of Gold Nanoparticles Supported on Hybrid Polymer/Metal Oxide as Catalysts for p-Chloronitrobenzene Hydrogenation

    Directory of Open Access Journals (Sweden)

    Cristian H. Campos

    2017-01-01

    Full Text Available This contribution reports a novel preparation of gold nanoparticles on polymer/metal oxide hybrid materials (Au/P[VBTACl]-M metal: Al, Ti or Zr and their use as heterogeneous catalysts in liquid phase hydrogenation of p-chloronitrobenzene. The support was prepared by in situ radical polymerization/sol gel process of (4-vinyl-benzyltrimethylammonium chloride and 3-(trimethoxysilylpropyl methacrylate in conjunction with metal-alkoxides as metal oxide precursors. The supported catalyst was prepared by an ion exchange process using chloroauric acid (HAuCl4 as gold precursor. The support provided the appropriate environment to induce the spontaneous reduction and deposition of gold nanoparticles. The hybrid material was characterized. TEM and DRUV-vis results indicated that the gold forms spherical metallic nanoparticles and that their mean diameter increases in the sequence, Au/P[VBTACl]-Zr > Au/P[VBTACl]-Al > Au/P[VBTACl]-Ti. The reactivity of the Au catalysts toward the p-CNB hydrogenation reaction is attributed to the different particle size distributions of gold nanoparticles in the hybrid supports. The kinetic pseudo-first-order constant values for the catalysts in the hydrogenation reaction increases in the order, Au/P[VBTACl]-Al > Au/P[VBTACl]-Zr > Au/P[VBTACl]-Ti. The selectivity for all the catalytic systems was greater than 99% toward the chloroaniline target product. Finally the catalyst supported on the hybrid with Al as metal oxide could be reused at least four times without loss in activity or selectivity for the hydrogenation of p-CNB in ethanol as solvent.

  2. Determination of the Molar Volume of Hydrogen from the Metal-Acid Reaction: An Experimental Alternative.

    Science.gov (United States)

    de Berg, Kevin; Chapman, Ken

    1996-01-01

    Describes an alternative technique for determining the molar volume of hydrogen from the metal-acid reaction in which the metal sample is encased in a specially prepared cage and a pipette filler is used to fill an inverted burette with water. Eliminates some difficulties encountered with the conventional technique. (JRH)

  3. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene

    Science.gov (United States)

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O.; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik

    2016-10-01

    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

  4. Acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts for hydrodeoxygenation process

    Science.gov (United States)

    Lup, A. Ng K.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

    2018-03-01

    Hydrodeoxygenation is an oxygen removal process that occurs in the presence of hydrogen and catalysts. This study has shown the importance of acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts in having high hydrodeoxygenation activity and selectivity. These properties are required to ensure the catalyst has high affinity for C-O or C=O bonds and the capability for the adsorption and activation of H2 and O-containing compounds. A theoretical framework of temperature programmed desorption technique was also discussed for the quantitative understanding of these properties. By using NH3-TPD, the nature and abundance of acid sites of catalyst can be determined. By using H2-TPD, the nature and abundance of metallic sites can also be determined. The desorption activation energy could also be determined based on the Redhead analysis of TPD spectra with different heating rates.

  5. Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.

    Science.gov (United States)

    Li, Changkun; Grugel, Christian P; Breit, Bernhard

    2016-04-30

    A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

  6. Poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation

    Science.gov (United States)

    Rakap, Murat

    2015-02-01

    The catalytic use of highly efficient poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles (4.2 ± 1.9 nm) in the hydrolysis of ammonia-borane is reported. The catalyst is prepared by co-reduction of two metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. They are recyclable and highly active for hydrogen generation from the hydrolysis of ammonia-borane even at very low concentrations and temperature, providing a record numbers of average turnover frequency value (125 mol H2/mol cat.min-1) and maximum hydrogen generation rate (3468 L H2 min-1 (mol cat)-1). They also provide activation energy of 51.7 ± 2 kJ/mol for the hydrolysis of ammonia borane.

  7. Electrochemical Cobalt-Catalyzed C-H Activation.

    Science.gov (United States)

    Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

    2018-06-19

    Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metal hydride hydrogen compression: recent advances and future prospects

    Science.gov (United States)

    Yartys, Volodymyr A.; Lototskyy, Mykhaylo; Linkov, Vladimir; Grant, David; Stuart, Alastair; Eriksen, Jon; Denys, Roman; Bowman, Robert C.

    2016-04-01

    Metal hydride (MH) thermal sorption compression is one of the more important applications of the MHs. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units, are analyzed. The paper includes also a theoretical modelling of a two-stage compressor aimed at describing the performance of the experimentally studied systems, their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS and the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the MH compression in the overall development of the hydrogen-driven energy systems. The work is based on the analysis of the development of the technology in Europe, USA and South Africa.

  9. Hydrogen isotope exchange in a metal hydride tube

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, David B. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2014-09-01

    This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

  10. Hydrogen embrittlement of metals. A bibliography with abstracts. Search period covered: 1964--August 1975

    International Nuclear Information System (INIS)

    Smith, M.F.

    1975-10-01

    The research covers the hydrogen embrittlement of both ferrous and nonferrous metals and alloys and includes nuclear technology, aircraft metallurgy, mechanical properties, testing, electroplating, fatigue, corrosion and fracture. Contains 230 abstracts

  11. Mechanistic studies related to the metal catalyzed reduction of carbon monoxide to hydrocarbons. Final report, April 1, 1977-June 30, 1985

    International Nuclear Information System (INIS)

    Casey, C.P.

    1985-02-01

    Studies of compounds related to proposed intermediates in the hydrogenation of carbon monoxide over homogeneous and heterogeneous catalysts have been carried out. The synthesis, structure, and reactions of metal formyl compounds have been investigated. The synthesis and desproportionation reactions of hydroxymethyl metal compounds have been explored. Reactions involving interconversion of n 5 - and n'-C 5 H 5 organometallic compounds have been discovered. New synthetic routes to bimetallic compounds with bridging hydrocarbon ligands have been developed. The first bimetallic compound with a budging CH ligand has been prepared. The hydrocarbation reaction in which the CH bond of a bridging methylidyne complex adds across a carbon-carbon double bond has been discovered. New heterobimetallic compounds linked by a heterodifunctional ligand and heterobimetallic compounds with directly bonded early and late transition metals have been synthesized in a search for new CO hydrogenation catalysts. 36 refs

  12. Palladium mixed-metal surface-modified AB5-type intermetallides enhance hydrogen sorption kinetics

    Directory of Open Access Journals (Sweden)

    Roman V. Denys

    2010-09-01

    Full Text Available Surface engineering approaches were adopted in the preparation of advanced hydrogen sorption materials, based on ‘low-temperature’, AB5-type intermetallides. The approaches investigated included micro-encapsulation with palladium and mixed-metal mantles using electroless plating. The influence of micro-encapsulation on the surface morphology and kinetics of hydrogen charging were investigated. It was found that palladium-nickel (Pd-Ni co-deposition by electroless plating significantly improved the kinetics of hydrogen charging of the AB5-type intermetallides at low hydrogen pressure and temperature, after long-term pre-exposure to air. The improvement in the kinetics of hydrogen charging was credited to a synergistic effect between the palladium and nickel atoms in the catalytic mantle and the formation of an ‘interfacial bridge’ for hydrogen diffusion by the nickel atoms in the deposited layer. The developed surface-modified materials may find application in highly selective hydrogen extraction, purification, and storage from impure hydrogen feeds.

  13. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    Energy Technology Data Exchange (ETDEWEB)

    Stanger, Keith James [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-α-acetamidocinnamate (MAC), has the illustrated structure as established by 31P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]4, [Rh(COD)2]+BF4-, [Rh(COD)Cl]2, and RhCl3• 3H2O, adsorbed on SiO2 are optimally activated for toluene hydrogenation by pretreatment with H2 at 200 C. The same complexes on Pd-SiO2 are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH2)3s-]Re(O)(Me)(PPh3) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  14. Hydrogen storage using borohydrides

    International Nuclear Information System (INIS)

    Bernard BONNETOT; Laetitia LAVERSENNE

    2006-01-01

    The possibilities of hydrogen storage using borohydrides are presented and discussed specially in regard of the recoverable hydrogen amount and related to the recovering conditions. A rapid analysis of storage possibilities is proposed taking in account the two main ways for hydrogen evolution: the dehydrogenation obtained through thermal decomposition or the hydrolysis of solids or solutions. The recoverable hydrogen is related to the dehydrogenation conditions and the real hydrogen useful percentage is determined for each case of use. The high temperature required for dehydrogenation even when using catalyzed compounds lead to poor outlooks for this storage way. The hydrolysis conditions direct the chemical yield of the water consuming, and this must be related to the experimental conditions which rule the storage capacity of the 'fuel' derived from the borohydride. (authors)

  15. Understanding hydrogen sorption in a metal-organic framework with open-metal sites and amide functional groups

    KAUST Repository

    Pham, Tony T.

    2013-05-09

    Grand canonical Monte Carlo (GCMC) studies of the mechanism of hydrogen sorption in an rht-MOF known as Cu-TPBTM are presented. The MOF is a decorated/substituted isostructural analogue to the unembellished rht-MOF, PCN-61, that was studied previously [ Forrest, K. A.J. Phys. Chem. C 2012, 116, 15538-15549. ]. The simulations were performed using three different hydrogen potentials of increasing complexity. Simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values were in excellent agreement with the reported experimental data for only a polarizable model in one of four experimentally observed crystal structure configurations. The study demonstrates the ability of modeling to distinguish the differential sorption of distinct strucures; one configuration is found to be dominant due to favorable interactions with substrates. In addition, it was discovered that the presence of polar amide groups had a significant effect on the electrostatics of the Cu2+ ions and directs the low-pressure physisorption of hydrogen in the MOF. This is in contrast to what was observed in PCN-61, where an exterior copper ion had a higher relative charge and was the favored loading site. This tunability of the electrostatics of the copper ions via chemical substitution on the MOF framework can be explained by the presence of the negatively charged oxygen atom of the amide group that causes the interior Cu2+ ion to exhibit a higher positive charge through an inductive effect. Further, control simulations, taking advantage of the flexibility afforded by theoretical modeling, include artificially modified charges for both Cu2+ ions chosen equal to or with a higher charge on the exterior Cu2+ ion. This choice resulted in distinctly different hydrogen sorption characteristics in Cu-TPBTM with no direct sorption on the open-metal sites. Thus, this study demonstrates both the tunable nature of MOF platforms and the possibility for rational design of sorption

  16. Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2014-01-01

    Full Text Available A modulated synthesis of Zr-metal organic framework (Zr-MOF) with improved ease of handling and decreased reaction time is reported to yield highly crystalline Zr-MOF with well-defined octahedral shaped crystals for practical hydrogen storage...

  17. Early hydrogen water chemistry in the boiling water reactor: industry-first demonstration

    International Nuclear Information System (INIS)

    Garcia, Susan E.; Odell, Andrew D.; Giannelli, Joseph F.

    2012-09-01

    Hydrogen injection into the BWR feedwater during power operation has resulted in significant IGSCC reductions. Further, noble metal application (NMCA) during shutdown or On-line NobleChem TM (OLNC) during power operation has greatly reduced the required hydrogen injection rate by catalyzing the hydrogen-oxygen reaction on the metal surfaces, reducing the electrochemical corrosion potential (ECP) at operating temperature to well below the mitigation ECP of -230 mV (SHE) at reactor water hydrogen to oxidant (O 2 + H 2 O 2 ) molar ratios of ≥2. Since IGSCC rates increase markedly at reduced temperature, and the potential for crack initiation exists, additional crack mitigation was desired. To close this gap in mitigation, the EPRI BWR Startup ECP Reduction research and development program commenced in 2008 to undertake laboratory and feasibility studies for adding a reductant to the reactor water system during start-ups. Under this program, ECP reductions of noble metal treated stainless steel sufficient to mitigate IGSCC at startup temperatures were achieved in the laboratory in the absence of radiation at hydrogen, hydrazine and carbohydrazide to oxygen molar ratios of ≥ 2, ≥1.5 and ≥0.7, respectively. Based on the familiarity of operating BWRs with using hydrogen, a demonstration of hydrogen injection during the startup of an actual BWR using noble metals was planned. This process, named EHWC (Early Hydrogen Water Chemistry), differs from the HDS (Hydrogen During Startup) approach that has been successful in Japan in that HDS injects sufficient hydrogen for bulk oxidant reduction whereas EHWC injects a smaller amount of hydrogen, sufficient to achieve a hydrogen:oxidant molar ratio of at least two at noble metal treated surfaces. The industry-first EHWC demonstration was performed at Exelon's Peach Bottom 3 nuclear power plant in October 2011. Prior to EHWC, Peach Bottom 3 had one NMCA (October 1999) and five annual OLNC applications (starting in 2007

  18. Muon catalyzed fusion at very low temperature: A new target system

    International Nuclear Information System (INIS)

    Mulhauser, F.; Beveridge, J.L.; Marshall, G.M.

    1994-10-01

    Muon catalyzed fusion (μCF) processes are usually studied in gases or liquids. A new target system allows experiments on muonic hydrogen isotopes in solid hydrogen layers at 3K, where processes of the μCF cycle can be separated and the energy dependence of reactions can be measured. Muonic tritium atomic beams with energy of the order of 1 eV have been produced via transfer and emission from solid hydrogen target containing small tritium concentrations. The μt energy distribution overlaps the predicted muonic molecular (dμt) formation resonances. Preliminary time of flight results are shown. (author). 9 refs., 5 figs

  19. Redox potential monitoring as a method to control unwanted noble metal-catalyzed hydrogen generation from formic acid treatment of simulated nuclear waste media

    International Nuclear Information System (INIS)

    King, R.B.; Bhattacharyya, N.K.

    1998-01-01

    Simulants for the Hanford Waste Vitrification Plant feed containing the major nonradioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 - , and NO 2 - were used to study redox potential changes in reactions of formic acid at 90 C catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Such reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase and a redox electrode to follow redox potential changes as a function of time. In the initial phase of formic acid addition to nitrite-containing feed simulants, the redox potential of the reaction mixture rises typically to +400 mV relative to the Al/AgCl electrode because of the generation of the moderately strongly oxidizing nitrous acid. No H 2 production occurs at this stage of the reaction as long as free nitrous acid is present. After all of the nitrous acid has been destroyed by reduction to N 2 O and NO and disproportionation to NO/NO 3 - , the redox potential of the reaction mixture becomes more negative than the Ag/AgCl electrode. The experiments outlined in this paper suggest the feasibility of controlling the production of H 2 by limiting the amount of formic acid used and monitoring the redox potential during formic acid treatment

  20. Modelling of fatigue crack propagation assisted by gaseous hydrogen in metallic materials

    International Nuclear Information System (INIS)

    Moriconi, C.

    2012-01-01

    Experimental studies in a hydrogenous environment indicate that hydrogen created by surface reactions, then drained into the plastic zone, leads to a modification of deformation and damage mechanisms at the fatigue crack tip in metals, resulting in a significant decrease of crack propagation resistance. This study aims at building a model of these complex phenomena in the framework of damage mechanics, and to confront it with the results of fatigue crack propagation tests in high pressure hydrogen on a 15-5PH martensitic stainless steel. To do so, a cohesive zone model was implemented in the finite element code ABAQUS. A specific traction-separation law was developed, which is suitable for cyclic loadings, and whose parameters depend on local hydrogen concentration. Furthermore, hydrogen diffusion in the bulk material takes into account the influence of hydrostatic stress and trapping. The mechanical behaviour of the bulk material is elastic-plastic. It is shown that the model can qualitatively predict crack propagation in hydrogen under monotonous loadings; then, the model with the developed traction-separation law is tested under fatigue loading. In particular, the simulated crack propagation curves without hydrogen are compared to the experimental crack propagation curves for the 15-5PH steel in air. Finally, simulated fatigue crack propagation rates in hydrogen are compared to experimental measurements. The model's ability to assess the respective contributions of the different damage mechanisms (HELP, HEDE) in the degradation of the crack resistance of the 15-5PH steel is discussed. (author)

  1. Develop improved metal hydride technology for the storage of hydrogen. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    Sapru, K.

    1998-12-04

    The overall objective was to develop commercially viable metal hydrides capable of reversibly storing at least 3 wt.% hydrogen for use with PEM fuel cells and hydrogen fueled internal combustion engine (HICE) applications. Such alloys are expected to result in system capacities of greater than 2 wt.%, making metal hydride storage systems (MHSS`s) a practical means of supplying hydrogen for many consumer applications. ECD`s (Energy Conversion Devices, Inc.) past work on sputtered thin films of transition metal-based alloys led to the commercialization of it`s nickel/metal hydride batteries, and similar work on thin film Mg-based alloys demonstrated potential to achieve very high gravimetric and volumetric energy densities approaching 2,500 Wh/Kg and 2,500 Wh/M{sup 3} respectively. Under this 2-year cost shared project with the DOE, the authors have successfully demonstrated the feasibility of scaling up the Mg-based hydrides from thin film to bulk production without substantial loss of storage capacity. ECD made progress in alloy development by means of compositional and process modification. Processes used include Mechanical Alloying, Melt spinning and novel Gas Phase Condensation. It was showed that the same composition when prepared by melt-spinning resulted in a more homogeneous material having a higher PCT plateau pressure as compared to mechanical alloying. It was also shown that mechanically alloyed Mg-Al-Zn results in much higher plateau pressures, which is an important step towards reducing the desorption temperature. While significant progress has been made during the past two years in alloy development and understanding the relationship between composition, structure, morphology, and processing parameters, additional R and D needs to be performed to achieve the goals of this work.

  2. Novel Dry-Type Glucose Sensor Based on a Metal-Oxide-Semiconductor Capacitor Structure with Horseradish Peroxidase + Glucose Oxidase Catalyzing Layer

    Science.gov (United States)

    Lin, Jing-Jenn; Wu, You-Lin; Hsu, Po-Yen

    2007-10-01

    In this paper, we present a novel dry-type glucose sensor based on a metal-oxide-semiconductor capacitor (MOSC) structure using SiO2 as a gate dielectric in conjunction with a horseradish peroxidase (HRP) + glucose oxidase (GOD) catalyzing layer. The tested glucose solution was dropped directly onto the window opened on the SiO2 layer, with a coating of HRP + GOD catalyzing layer on top of the gate dielectric. From the capacitance-voltage (C-V) characteristics of the sensor, we found that the glucose solution can induce an inversion layer on the silicon surface causing a gate leakage current flowing along the SiO2 surface. The gate current changes Δ I before and after the drop of glucose solution exhibits a near-linear relationship with increasing glucose concentration. The Δ I sensitivity is about 1.76 nA cm-2 M-1, and the current is quite stable 20 min after the drop of the glucose solution is tested.

  3. Preparation of Pt/USY catalysers and application in the reformation of n-octane; Preparacao de catalisadores Pt/USY e aplicacao na reforma do n-octano

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, Alfredina dos S.; Sousa, Bianca V.; Grau, Javier M.; Rodrigues, Meiry Glaucia F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil)

    2008-07-01

    During the catalytic reform, the hydrocarbons of long chain are reconstructed, through reactions of isomerization, hydrogenation, desidrocyclization and dehydrogenation, among others. These reactions occur in acid or metallic small farms, on a bifunctional catalyzer of type Pt/Al{sub 2}O{sub 3}-Cl. The metallic component is active in the hydrogenation and dehydrogenation, while the support (chlorinated alumine) possess acidity enough to promote isomerization reactions. The joint action of the two small farms promotes other reactions, as the desidrocyclization, through a bifunctional mechanism. Reactions also occur undesirable (hydrocracking and hydrogenation) that they diminish the selectivity and they deactivate the catalyzer for coke formation. The catalyzers most promising for this reaction are the acid zeolites of great pores, had to its textural characteristics that facilitate the access of the reagents to active small farms. In this work, the catalytic performance of the metallic function in the dehydrogenation reaction, the conversion and income in the reaction of reform of n-octane will be studied, of the catalyzers of the Pt/USY type. (author)

  4. Metal-Catalyzed Intra- and Intermolecular Addition of Carboxylic Acids to Alkynes in Aqueous Media: A Review

    Directory of Open Access Journals (Sweden)

    Javier Francos

    2017-11-01

    Full Text Available The metal-catalyzed addition of carboxylic acids to alkynes is a very effective tool for the synthesis of carboxylate-functionalized olefinic compounds in an atom-economical manner. Thus, a large variety of synthetically useful lactones and enol-esters can be accessed through the intra- or intermolecular versions of this process. In order to reduce the environmental impact of these reactions, considerable efforts have been devoted in recent years to the development of catalytic systems able to operate in aqueous media, which represent a real challenge taking into account the tendency of alkynes to undergo hydration in the presence of transition metals. Despite this, different Pd, Pt, Au, Cu and Ru catalysts capable of promoting the intra- and intermolecular addition of carboxylic acids to alkynes in a selective manner in aqueous environments have appeared in the literature. In this review article, an overview of this chemistry is provided. The synthesis of β-oxo esters by catalytic addition of carboxylic acids to terminal propargylic alcohols in water is also discussed.

  5. Enhancing hydrogen spillover and storage

    Science.gov (United States)

    Yang, Ralph T [Ann Arbor, MI; Li, Yingwel [Ann Arbor, MI; Lachawiec, Jr., Anthony J.

    2011-05-31

    Methods for enhancing hydrogen spillover and storage are disclosed. One embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the hydrogen receptor to ultrasonification as doping occurs. Another embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the doped hydrogen receptor to a plasma treatment.

  6. Support Effects in the Gold-Catalyzed Preferential Oxidation of CO

    KAUST Repository

    Ivanova, S.

    2010-04-08

    The study of support effects on the gold-catalyzed preferential oxidation of carbon monoxide in the presence of hydrogen (PROX reaction) is possible only with careful control of the gold particle size, which is facilitated by the application of the direct anionic exchange method. Catalytic evaluation of thermally stable gold nanoparticles, with an average size of around 3 nm on a variety of supports (alumina, titania, zirconia, or ceria), clearly shows that the influence of the support on the CO oxidation rate is of primary importance under CO+O 2 conditions and that this influence becomes secondary in the presence of hydrogen. The impact of the support surface structure on the oxidation rates, catalyst selectivity, and catalyst activation/deactivation is investigated in terms of oxygen vacancies, oxygen mobility, OH groups, and surface area on the oxidation rates, catalyst selectivity and catalyst activation/deactivation. It allows the identification of key morphological and structural features of the support to ensure high activity and selectivity in the gold-catalyzed PROX reaction. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Performance study of a hydrogen powered metal hydride actuator

    International Nuclear Information System (INIS)

    Bhuiya, Md Mainul Hossain; Kim, Kwang J

    2016-01-01

    A thermally driven hydrogen powered actuator integrating metal hydride hydrogen storage reactor, which is compact, noiseless, and able to generate smooth actuation, is presented in this article. To test the plausibility of a thermally driven actuator, a conventional piston type actuator was integrated with LaNi 5 based hydrogen storage system. Copper encapsulation followed by compaction of particles into pellets, were adopted to improve overall thermal conductivity of the reactor. The operation of the actuator was thoroughly investigated for an array of operating temperature ranges. Temperature swing of the hydride reactor triggering smooth and noiseless actuation over several operating temperature ranges were monitored for quantification of actuator efficiency. Overall, the actuator generated smooth and consistent strokes during repeated cycles of operation. The efficiency of the actuator was found to be as high as 13.36% for operating a temperature range of 20 °C–50 °C. Stress–strain characteristics, actuation hysteresis etc were studied experimentally. Comparison of stress–strain characteristics of the proposed actuator with traditional actuators, artificial muscles and so on was made. The study suggests that design modification and use of high pressure hydride may enhance the performance and broaden the application horizon of the proposed actuator in future. (paper)

  8. 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.

  9. Hydrogen evolution activity and electrochemical stability of selected transition metal carbides in concentrated phosphoric acid

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Jensen, Jens Oluf; Bjerrum, Niels J.

    2014-01-01

    phosphoric acid were investigated in a temperature range from 80 to 170°C. A significant dependence of the activities on temperature was observed for all five carbide samples. Through the entire temperature range Group 6 metal carbides showed higher activity than that of the Group 5 metal carbides......Alternative catalysts based on carbides of Group 5 (niobium and tantalum) and 6 (chromium, molybdenum and tungsten) metals were prepared as films on the metallic substrates. The electrochemical activities of these carbide electrodes towards the hydrogen evolution reaction (HER) in concentrated...

  10. [The effect of hydrogen peroxide on the electrochemical corrosion properties and metal ions release of nickel-chromium dental alloys].

    Science.gov (United States)

    Wang, Jue; Qiao, Guang-yan

    2013-04-01

    To investigate the effect of hydrogen peroxide on the electrochemical corrosion and metal ions release of nickel-chromium dental alloys. The corrosion resistance of nickel-chromium dental alloys was compared by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curve (PD) methods in artificial saliva after immersed in different concentrations of hydrogen peroxide for 112 h. The metal ions released from nickel-chromium dental alloys to the artificial saliva were detected after electrochemical measurements using inductively coupled plasma mass spectrometry (ICP-MS). The data was statistically analyzed by analysis of variance (ANOVA) using SPSS 13.0 software package. The electrochemical experiment showed that the sequence of polarization resistance in equivalent circuit (Rct), corrosion potential (Ecorr), pitting breakdown potential (Eb), and the difference between Ecorr and Eb representing the "pseudo-passivation" (δE) of nickel-chromium alloys in artificial saliva was 30% alloys to the artificial saliva, and the order of the concentrations of metal ions was 0% corrosion resistance of nickel-chromium dental alloys decrease after immersed in different concentrations of hydrogen peroxide for 112 h. Nickel-chromium dental alloys are more prone to corrosion in the artificial saliva with the concentration of hydrogen peroxide increased, and more metal ions are released in the artificial saliva.

  11. Lactam hydrolysis catalyzed by mononuclear metallo-ß-bactamases

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U

    2003-01-01

    Two central steps in the hydrolysis of lactam antibiotics catalyzed by mononuclear metallo-beta-lactamases, formation of the tetrahedral intermediate and its breakdown by proton transfer, are studied for model systems using the density functional B3LYP method. Metallo-beta-lactamases have two metal...

  12. First principles calculations and experimental insight into methane steam reforming over transition metal catalysts

    DEFF Research Database (Denmark)

    Jones, Glenn; Jakobsen, Jon Geest; Shim, Signe Sarah

    2008-01-01

    This paper presents a detailed analysis of the steam reforming process front first-principles calculations, supported by insight from experimental investigations. In the present work we employ recently recognised scaling relationships for adsorption energies of simple molecules adsorbed at pure...... metal Surfaces to develop an overview of the steam reforming process catalyzed by a range of transition metal surfaces. By combining scaling relationships with thermodynamic and kinetic analysis, we show that it is possible to determine the reactivity trends of the pure metals for methane steam...... in situ TEM measurements under a hydrogen atmosphere. The overall agreement between theory and experiment (at 773 K, 1 bar pressure and 10% conversion) is found to be excellent with Ru and Rh being the most active pure transition metals for methane steam reforming, while Ni, Ir, Pt, and Pd...

  13. Adsorption of hydrogen on clean and modified magnesium films

    DEFF Research Database (Denmark)

    Johansson, Martin; Ostenfeld, Christopher Worsøe; Chorkendorff, Ib

    2006-01-01

    films at H/Mg ratios less than 2% is developed. The activation barrier for hydrogen dissociation is 72 +/- 15 kJ/mole H-2, and a stagnant hydrogen uptake is observed. For platinum-catalyzed films, the barrier is significantly reduced, and there is no stagnation in the uptake rate....

  14. Method for the enzymatic production of hydrogen

    Science.gov (United States)

    Woodward, J.; Mattingly, S.M.

    1999-08-24

    The present invention is an enzymatic method for producing hydrogen comprising the steps of: (a) forming a reaction mixture within a reaction vessel comprising a substrate capable of undergoing oxidation within a catabolic reaction, such as glucose, galactose, xylose, mannose, sucrose, lactose, cellulose, xylan and starch; the reaction mixture also comprising an amount of glucose dehydrogenase in an amount sufficient to catalyze the oxidation of the substrate, an amount of hydrogenase sufficient to catalyze an electron-requiring reaction wherein a stoichiometric yield of hydrogen is produced, an amount of pH buffer in an amount sufficient to provide an environment that allows the hydrogenase and the glucose dehydrogenase to retain sufficient activity for the production of hydrogen to occur and also comprising an amount of nicotinamide adenine dinucleotide phosphate sufficient to transfer electrons from the catabolic reaction to the electron-requiring reaction; (b) heating the reaction mixture at a temperature sufficient for glucose dehydrogenase and the hydrogenase to retain sufficient activity and sufficient for the production of hydrogen to occur, and heating for a period of time that continues until the hydrogen is no longer produced by the reaction mixture, wherein the catabolic reaction and the electron-requiring reactions have rates of reaction dependent upon the temperature; and (c) detecting the hydrogen produced from the reaction mixture. 8 figs.

  15. Infrared studies of ortho-para conversion at Cl-atom and H-atom impurity centers in cryogenic solid hydrogen

    International Nuclear Information System (INIS)

    Raston, P.L.; Kettwich, S.C.; Anderson, D.T.

    2010-01-01

    We report infrared spectroscopic studies of H 2 ortho-para (o/p) conversion in solid hydrogen doped with Cl-atoms at 2 K while the Cl + H 2 (υ = 1) → HCl + H infrared-induced chemical reaction is occurring. The Cl-atom doped hydrogen crystals are synthesized using 355 nm in situ photodissociation of Cl 2 precursor molecules. For hydrogen solids with high ortho-H 2 fractional concentrations (X o = 0.55), the o/p conversion kinetics is dominated by Cl-atom catalyzed conversion with a catalyzed conversion rate constant K cc = 1.16(11) min -1 and the process is rate-limited by ortho-H 2 quantum diffusion. For hydrogen crystals with low ortho-H2 concentrations (X o = 0.03), single-exponential decay of the ortho-H 2 concentration with time is observed which is attributed to H-atom catalyzed o/p conversion by the H-atoms produced during the infrared-induced Cl + H 2 reaction. The measured H-atom catalyzed o/p conversion kinetics indicates the H-atoms are mobile under these conditions in agreement with previous ESR measurements.

  16. OPTIMIZATION OF INTERNAL HEAT EXCHANGERS FOR HYDROGEN STORAGE TANKS UTILIZING METAL HYDRIDES

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, S.; Tamburello, D.; Hardy, B.; Anton, D.; Gorbounov, M.; Cognale, C.; van Hassel, B.; Mosher, D.

    2011-07-14

    Two detailed, unit-cell models, a transverse fin design and a longitudinal fin design, of a combined hydride bed and heat exchanger are developed in COMSOL{reg_sign} Multiphysics incorporating and accounting for heat transfer and reaction kinetic limitations. MatLab{reg_sign} scripts for autonomous model generation are developed and incorporated into (1) a grid-based and (2) a systematic optimization routine based on the Nelder-Mead downhill simplex method to determine the geometrical parameters that lead to the optimal structure for each fin design that maximizes the hydrogen stored within the hydride. The optimal designs for both the transverse and longitudinal fin designs point toward closely-spaced, small cooling fluid tubes. Under the hydrogen feed conditions studied (50 bar), a 25 times improvement or better in the hydrogen storage kinetics will be required to simultaneously meet the Department of Energy technical targets for gravimetric capacity and fill time. These models and methodology can be rapidly applied to other hydrogen storage materials, such as other metal hydrides or to cryoadsorbents, in future work.

  17. Nuclear spin relaxation due to hydrogen diffusion in b.c.c. metals

    International Nuclear Information System (INIS)

    Faux, D.A.; Hall, C.K.

    1989-01-01

    We present Monte Carlo simulation results for the proton-proton contribution to the T 1 -1 relaxation rate for hydrogen spins diffusing on the tetrahedral sites of a b.c.c. metal. It is assumed that each hydrogen blocks all sites to the zeroth (no multiple-occupancy), second or third neighbour and that longer-range interactions may be neglected. Comparisons are made to the BPP and Torrey models. It is found that both the BPP and Torrey models give reasonable values for the peak height but that their predictions for the peak position and the high- and low-temperature limit are in error, particularly for large blocking distances. (orig.)

  18. Metal hydride hydrogen and heat storage systems as enabling technology for spacecraft applications

    Energy Technology Data Exchange (ETDEWEB)

    Reissner, Alexander, E-mail: reissner@fotec.at [FOTEC Forschungs- und Technologietransfer GmbH, Viktor Kaplan Straße 2, 2700 Wiener Neustadt (Austria); University of Applied Sciences Wiener Neustadt, Johannes Gutenberg-Straße 3, 2700 Wiener Neustadt (Austria); Pawelke, Roland H.; Hummel, Stefan; Cabelka, Dusan [FOTEC Forschungs- und Technologietransfer GmbH, Viktor Kaplan Straße 2, 2700 Wiener Neustadt (Austria); Gerger, Joachim [University of Applied Sciences Wiener Neustadt, Johannes Gutenberg-Straße 3, 2700 Wiener Neustadt (Austria); Farnes, Jarle, E-mail: Jarle.farnes@prototech.no [CMR Prototech AS, Fantoftvegen 38, PO Box 6034, 5892 Bergen (Norway); Vik, Arild; Wernhus, Ivar; Svendsen, Tjalve [CMR Prototech AS, Fantoftvegen 38, PO Box 6034, 5892 Bergen (Norway); Schautz, Max, E-mail: max.schautz@esa.int [European Space Agency, ESTEC – Keplerlaan 1, 2201 AZ Noordwijk Zh (Netherlands); Geneste, Xavier, E-mail: xavier.geneste@esa.int [European Space Agency, ESTEC – Keplerlaan 1, 2201 AZ Noordwijk Zh (Netherlands)

    2015-10-05

    Highlights: • A metal hydride tank concept for heat and hydrogen storage is presented. • The tank is part of a closed-loop reversible fuel cell system for space application. • For several engineering issues specific to the spacecraft application, solutions have been developed. • The effect of water contamination has been approximated for Ti-doped NaAlH{sub 4}. • A novel heat exchanger design has been realized by Selective Laser Melting. - Abstract: The next generation of telecommunication satellites will demand a platform payload performance in the range of 30+ kW within the next 10 years. At this high power output, a Regenerative Fuel Cell Systems (RFCS) offers an efficiency advantage in specific energy density over lithium ion batteries. However, a RFCS creates a substantial amount of heat (60–70 kJ per mol H{sub 2}) during fuel cell operation. This requires a thermal hardware that accounts for up to 50% of RFCS mass budget. Thus the initial advantage in specific energy density is reduced. A metal hydride tank for combined storage of heat and hydrogen in a RFCS may overcome this constraint. Being part of a consortium in an ongoing European Space Agency project, FOTEC is building a technology demonstrator for such a combined hydrogen and heat storage system.

  19. Hydrogen chemisorption and oxidation of transition metal carbides

    International Nuclear Information System (INIS)

    Bethin, J.R.

    1979-01-01

    A study was made of the catalytic activity of WC, focusing on the possible influence of point defects. The chemisorption of H on WC and titanium oxycarbides was studied with differential scanning calorimetry. The catalytic activity of these materials for oxidation of H was determined by potentiostatic steady-state and potentiodynamic measurements in acid electrolyte. Compositions of WC surfaces were determined by x-ray photoemission and related to the catalytic behavior. Titanium oxycarbide surfaces were analyzed by Auger electron spectroscopy. Of the carbides tested only one WC preparation was able to chemisorb H. Both WC powders investigated catalyzed H oxidation with similar specific activities. Spectroscopic studies showed that the active surface of WC was a mixture of WO 3 and a carbon-deficient WC phase. This result indicates that carbon vacancies are the active sites in tungsten carbide. Theoretical models of a carbon vacancy surrounded by metal atoms suggested by calculations by other workers support this assignment and identify the important role of the W6s level. The measured value of the heat of chemisorption is consistent with the proposed model

  20. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

    Science.gov (United States)

    Jia, Hong-Peng; Quadrelli, Elsje Alessandra

    2014-01-21

    Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

  1. The effect of co-deposition of hydrogen and metals on wall pumping in long duration plasma in TRIAM-1M

    International Nuclear Information System (INIS)

    Miyamoto, M.; Tokitani, M.; Tokunaga, K.; Fujiwara, T.; Yoshida, N.; Sakamoto, M.; Zushi, H.; Nagata, S.; Ono, K.

    2005-01-01

    The effect of co-deposition on recycling and wall pumping during long duration plasmas in TRIAM-1M has been studied. To examine the hydrogen retention on the all metal walls, material exposure experiments were carried out using an ultra-long discharge for about 72 min. After exposure to the plasma, the surface modification and hydrogen retention of the specimens were examined quantitatively by means of ion beam analysis techniques and transmission electron microscopy (TEM). Large amount of retained hydrogen were detected in the specimen exposed to the long duration discharge in TRIAM-1M. This amount was sufficient to explain the wall pumping in TRIAM-1M. A correlation was also observed between the thicknesses of the deposits and the amount of retained hydrogen. These results mean that the metallic deposited layer can trap a large amount of hydrogen and has a strong influence on hydrogen recycling similar to a carbon deposit

  2. Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

    Science.gov (United States)

    Huang, Cunping (Inventor); T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor)

    2014-01-01

    Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

  3. Catalytic Metal Free Production of Large Cage Structure Carbon Particles: A Candidate for Hydrogen Storage

    Science.gov (United States)

    Kimura, Yuki; Nuth, Joseph A., III; Ferguson, Frank T.

    2005-01-01

    We will demonstrate that carbon particles consisting of large cages can be produced without catalytic metal. The carbon particles were produced in CO gas as well as by introduction of 5% methane gas into the CO gas. The gas-produced carbon particles were able to absorb approximately 16.2 wt% of hydrogen. This value is 2.5 times higher than the 6.5 wt% goal for the vehicular hydrogen storage proposed by the Department of Energy in the USA. Therefore, we believe that this carbon particle is an excellent candidate for hydrogen storage for fuel cells.

  4. High density hydrogen research

    International Nuclear Information System (INIS)

    Hawke, R.S.

    1977-01-01

    The interest in the properties of very dense hydrogen is prompted by its abundance in Saturn and Jupiter and its importance in laser fusion studies. Furthermore, it has been proposed that the metallic form of hydrogen may be a superconductor at relatively high temperatures and/or exist in a metastable phase at ambient pressure. For ten years or more, laboratories have been developing the techniques to study hydrogen in the megabar region (1 megabar = 100 GPa). Three major approaches to study dense hydrogen experimentally have been used, static presses, shockwave compression, and magnetic compression. Static tchniques have crossed the megabar threshold in stiff materials but have not yet been convincingly successful in very compressible hydrogen. Single and double shockwave techniques have improved the precision of the pressure, volume, temperature Equation of State (EOS) of molecular hydrogen (deuterium) up to near 1 Mbar. Multiple shockwave and magnetic techniques have compressed hydrogen to several megabars and densities in the range of the metallic phase. The net result is that hydrogen becomes conducting at a pressure between 2 and 4 megabars. Hence, the possibility of making a significant amount of hydrogen into a metal in a static press remains a formidable challenge. The success of such experiments will hopefully answer the questions about hydrogen's metallic vs. conducting molecular phase, superconductivity, and metastability. 4 figures, 15 references

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

    International Nuclear Information System (INIS)

    McCue, Jeffrey M.; Driscoll, William J.; Mueller, Gregory P.

    2008-01-01

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

  6. Improved metal-adhesive polymers from copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Accurso, Adrian A; Delaney, Mac; O'Brien, Jeff; Kim, Hyonny; Iovine, Peter M; Díaz Díaz, David; Finn, M G

    2014-08-18

    Electrically conductive adhesive polymers offer many potential advantages relative to Sn-Pb solders, including reduced toxicity, low cost, low processing temperatures, and the ability to make application-specific formulations. Polymers generated from the copper(I)-catalyzed cycloaddition (CuAAC) reaction between multivalent azides and alkynes have previously been identified as strong metal-binding adhesives. Herein we demonstrate that the performance of these materials can be remarkably improved by the incorporation of a flexibility-inducing difunctionalized component and a tertiary amine additive in optimized concentrations. The best formulations were identified by means of rapid adhesion testing of a library of potential candidates by using a custom-built instrument and validated in an American Society for Testing and Materials (ASTM)-standard lap-shear test. Characteristic phase transitions were identified by differential scanning calorimetry (DSC) for adhesives with and without the additives as a function of curing temperature. The incorporation of flexible components was found to more than double the strength of the adhesive. Moreover, the adhesive was made electrically conductive by the inclusion of 20 wt% silver-coated copper flakes and further improved in this regard by the incorporation of multiwalled carbon nanotubes in the formulation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of a novel chemotype via sequential metal-catalyzed cycloisomerizations

    Directory of Open Access Journals (Sweden)

    Bo Leng

    2012-08-01

    Full Text Available Sequential cycloisomerizations of diynyl o-benzaldehyde substrates to access novel polycyclic cyclopropanes are reported. The reaction sequence involves initial Cu(I-mediated cycloisomerization/nucleophilic addition to an isochromene followed by diastereoselective Pt(II-catalyzed enyne cycloisomerization.

  8. Radiological analysis by the addition of hydrogen and noble metals in the reactors of the Laguna Verde central

    International Nuclear Information System (INIS)

    Padilla C, I.

    2006-01-01

    During the operation of the nuclear power stations there are metals that are subject to condition and agents that cause that these they present indications of intergranular corrosion and for their importance they are subject to a continuous surveillance to assure their integrity. During the time of operation, for the level of indications, it can be necessary the substitution of these. The internal components of the vessel and particularly those of the structure of the reactor core are exposed during the operation to a neutron flow that causes that these they are activated and, in consequence, before an eventual repair it will be necessary to face high radiation levels. At the moment a technique that controls exists and it reduces the growth rate of the indications in the metals and it increases its useful life: the addition of hydrogen. The addition of hydrogen it is an ALARA measure from long term when protecting the internals of the vessel that requires to establish radiological controls in the stage of their application to avoid unnecessary dose to the personnel. The addition of hydrogen to the primary system has as objective to reduce the growth of indications taken place by intergranular corrosion in metals of the reactor core and this is achieved when the electrochemical thresholds are reached. Hydrogen to interacting with the metal surfaces it generates reductive reactions causing in consequence an increment in the concentration of soluble cobalt in the coolant one and an increment in the nitrogen concentration. To reduce the magnitude of the radiological impact that in some NC reach up to factors 10, its are injected to the system noble metals as the rhodium and the platinum, to reduce the concentration of hydrogen to the system and to be below the threshold electrochemical potential necessary to protect the internals of the reactor vessel. The external and internal operational experience generated on this protection technique to the internals of the vessel

  9. Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian

    2014-01-01

    The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well-known aqueous...... reaction mechanism. The energy barrier of the catalyzed amidation reaction is approximately 40 kJ mol(-1) lower than the non-catalyzed amidation reaction. At least partially this can be explained by a hydrogen bond from the amine to the π-electrons of the thiophenol, stabilizing the transition state...

  10. Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

    Science.gov (United States)

    Viditha, V; Srilatha, K; Himabindu, V

    2016-05-01

    Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities.

  11. Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

    Science.gov (United States)

    Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

    2015-10-27

    The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

  12. Inspection of the hydrogen gas pressure with metal shield by cold neutron radiography at CMRR

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hang; Cao, Chao; Huo, Heyong; Wang, Sheng; Wu, Yang; Yin, Wei; Sun, Yong; Liu, Bin; Tang, Bin [Institute of Nuclear Physics and Chemistry, Chinese Academy of Engineering Physics, Mianyang (China); Key Laboratory of Neutron Physics, Chinese Academy of Engineering Physics, Mianyang (China)

    2017-04-11

    The inspection of the process of gas pressure change is important for some applications (e.g. gas tank stockpile or two phase fluid model) which need quantitative and non-touchable measurement. Neutron radiography provides a suitable tool for such investigations with nice resolution. The quantitative cold neutron radiography (CNR) is developed at China Mianyang Research Reactor (CMRR) to measure the hydrogen gas pressure with metal shield. Because of the high sensitivity to hydrogen, even small change of the hydrogen pressure can be inspected by CNR. The dark background and scattering neutron effect are both corrected to promote measurement precision. The results show that CNR can measure the hydrogen gas pressure exactly and the pressure value average relative error between CNR and barometer is almost 1.9%.

  13. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage.

    Science.gov (United States)

    Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J

    2016-02-23

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.

  14. Renewable Molecular Flasks with NADH Models: Combination of Light-Driven Proton Reduction and Biomimetic Hydrogenation of Benzoxazinones.

    Science.gov (United States)

    Zhao, Liang; Wei, Jianwei; Lu, Junhua; He, Cheng; Duan, Chunying

    2017-07-17

    Using small molecules with defined pockets to catalyze chemical transformations resulted in attractive catalytic syntheses that echo the remarkable properties of enzymes. By modulating the active site of a nicotinamide adenine dinucleotide (NADH) model in a redox-active molecular flask, we combined biomimetic hydrogenation with in situ regeneration of the active site in a one-pot transformation using light as a clean energy source. This molecular flask facilitates the encapsulation of benzoxazinones for biomimetic hydrogenation of the substrates within the inner space of the flask using the active sites of the NADH models. The redox-active metal centers provide an active hydrogen source by light-driven proton reduction outside the pocket, allowing the in situ regeneration of the NADH models under irradiation. This new synthetic platform, which offers control over the location of the redox events, provides a regenerating system that exhibits high selectivity and efficiency and is extendable to benzoxazinone and quinoxalinone systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Palladium(II)-catalyzed oxidation of L-tryptophan by ...

    Indian Academy of Sciences (India)

    dium(II)] were obtained. The reaction exhibits fractional-second order kinetics with respect to [H ... compounds. Its use- fulness may be due to its unequivocal stability, water. ∗ ... metals are known to catalyze many oxidation–reduction reactions because they ... prepared by dissolving potassium hexacyanoferrate(II). (SD Fine ...

  16. Hydrogen storage for fuel cell applications: Challenges, opportunities and prospects for metal-organic frameworks

    CSIR Research Space (South Africa)

    Langmi, Henrietta W

    2013-07-01

    Full Text Available and release, and cycle life of the materials. In the past decade, there has been growing interest in metal organic frameworks (MOFs) as hydrogen storage materials and significant progress has been made in this regard. The challenges, opportunities...

  17. Scaled Testing of Hydrogen Gas Getters for Transuranic Waste

    International Nuclear Information System (INIS)

    Kaszuba, J.; Mroz, E.; Haga, M.; Hollis, W. K.; Peterson, E.; Stone, M.; Orme, C.; Luther, T.; Benson, M.

    2006-01-01

    Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage and shipment containers. Hydrogen forms a flammable mixture with air over a wide range of concentrations (5% to 75%), and very low energy is needed to ignite hydrogen-air mixtures. For these reasons, the concentration of hydrogen in waste shipment containers (Transuranic Package Transporter-II or TRUPACT-II containers) needs to remain below the lower explosion limit of hydrogen in air (5 vol%). Accident scenarios and the resulting safety analysis require that this limit not be exceeded. The use of 'hydrogen getters' is being investigated as a way to prevent the build up of hydrogen in TRUPACT-II containers. Preferred getters are solid materials that scavenge hydrogen from the gas phase and chemically and irreversibly bind it into the solid state. In this study, two getter systems are evaluated: a) 1,4-bis (phenylethynyl)benzene or DEB, characterized by the presence of carbon-carbon triple bonds; and b) a proprietary polymer hydrogen getter, VEI or TruGetter, characterized by carbon-carbon double bonds. Carbon in both getter types may, in the presence of suitable precious metal catalysts such as palladium, irreversibly react with and bind hydrogen. With oxygen present, the precious metal may also eliminate hydrogen by catalyzing the formation of water. This reaction is called catalytic recombination. DEB and VEI performed satisfactorily in lab scale tests using small test volumes (ml-scale), high hydrogen generation rates, and short time spans of hours to days. The purpose of this study is to evaluate whether DEB and VEI perform satisfactorily in actual drum-scale tests with realistic hydrogen generation rates and time frames. The two getter systems were evaluated in test vessels comprised of a Gas Generation Test Program-style bell-jar and a drum equipped with a composite drum filter. The vessels were scaled to replicate the ratio between void space in the

  18. Microbially catalyzed nitrate-dependent metal/radionuclide oxidation in shallow subsurface sediments

    Science.gov (United States)

    Weber, K.; Healy, O.; Spanbauer, T. L.; Snow, D. D.

    2011-12-01

    Anaerobic, microbially catalyzed nitrate-dependent metal/radionuclide oxidation has been demonstrated in a variety of sediments, soils, and groundwater. To date, studies evaluating U bio-oxidation and mobilization have primarily focused on anthropogenically U contaminated sites. In the Platte River Basin U originating from weathering of uranium-rich igneous rocks in the Rocky Mountains was deposited in shallow alluvial sediments as insoluble reduced uranium minerals. These reduced U minerals are subject to reoxidation by available oxidants, such nitrate, in situ. Soluble uranium (U) from natural sources is a recognized contaminant in public water supplies throughout the state of Nebraska and Colorado. Here we evaluate the potential of anaerobic, nitrate-dependent microbially catalyzed metal/radionuclide oxidation in subsurface sediments near Alda, NE. Subsurface sediments and groundwater (20-64ft.) were collected from a shallow aquifer containing nitrate (from fertilizer) and natural iron and uranium. The reduction potential revealed a reduced environment and was confirmed by the presence of Fe(II) and U(IV) in sediments. Although sediments were reduced, nitrate persisted in the groundwater. Nitrate concentrations decreased, 38 mg/L to 30 mg/L, with increasing concentrations of Fe(II) and U(IV). Dissolved U, primarily as U(VI), increased with depth, 30.3 μg/L to 302 μg/L. Analysis of sequentially extracted U(VI) and U(IV) revealed that virtually all U in sediments existed as U(IV). The presence of U(IV) is consistent with reduced Fe (Fe(II)) and low reduction potential. The increase in aqueous U concentrations with depth suggests active U cycling may occur at this site. Tetravalent U (U(IV)) phases are stable in reduced environments, however the input of an oxidant such as oxygen or nitrate into these systems would result in oxidation. Thus co-occurrence of nitrate suggests that nitrate could be used by bacteria as a U(IV) oxidant. Most probable number

  19. Solid State NMR Characterization of Complex Metal Hydrides systems for Hydrogen Storage Applications

    Directory of Open Access Journals (Sweden)

    Son-Jong Hwang

    2011-12-01

    Full Text Available Solid state NMR is widely applied in studies of solid state chemistries for hydrogen storage reactions. Use of 11B MAS NMR in studies of metal borohydrides (BH4 is mainly focused, revisiting the issue of dodecaborane formation and observation of 11B{1H} Nuclear Overhauser Effect.

  20. The generation of molecular hydrogen by cyanobacteria. Die Gewinnung von molekularem Wasserstoff durch Cyanobakterien

    Energy Technology Data Exchange (ETDEWEB)

    Kentemich, T.; Haverkamp, G.; Bothe, H. (Koeln Univ. (Germany, F.R.). Botanisches Inst.)

    1990-01-01

    Currently there is renewed interest in projects on solar-energy conversion by microorganisms. Among all organisms, cyanobacteria are first choice for such projects. Hydrogen production by cyanobacteria is light-dependent and catalyzed by the enzyme complex nitrogenase which concomitantly catalyzes the reduction of N{sub 2} to ammonia. The cyanobacterium Anabaena variabilis can express an alternative, vanadium-containing nitrogenase which produces more hydrogen than the conventional, molybdenum-containing enzyme. In intact cells, most of the H{sub 2} produced by nitrogenase is immediatley reutilized by the hydrogenase enzymes. Maximal hydrogen production requires the genetic blockage of H{sub 2} utilization by the hydrogenases. (orig.).

  1. Chemical bonding of hydrogen molecules to transition metal complexes

    International Nuclear Information System (INIS)

    Kubas, G.J.

    1990-01-01

    The complex W(CO) 3 (PR 3 ) 2 (H 2 ) (CO = carbonyl; PR 3 = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H 2 exchanges easily with D 2 . This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H 2 bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H 2 )(R 2 PCH 2 CH 2 PR 2 ) 2 were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig

  2. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

    Science.gov (United States)

    Corbin, Joshua R; Schomaker, Jennifer M

    2017-04-13

    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  3. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, Roman Vladimirovich [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  4. Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell.

    Science.gov (United States)

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D

    2012-11-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

  5. Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huamin; Lee, Suh-Jane; Olarte, Mariefel V.; Zacher, Alan H.

    2016-08-30

    Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenated to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was

  6. Double role of the hydroxy group of phosphoryl in palladium(II)-catalyzed ortho-olefination: a combined experimental and theoretical investigation.

    Science.gov (United States)

    Liu, Liu; Yuan, Hang; Fu, Tingting; Wang, Tao; Gao, Xiang; Zeng, Zhiping; Zhu, Jun; Zhao, Yufen

    2014-01-03

    Density functional theory calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dimethyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C-H bond activation, transmetalation, reductive elimination, and recycling of catalyst, each of which is constituted from different steps. Our calculations reveal that the hydroxy group of phosphoryl plays a crucial role almost in all steps, which can not only stabilize the intermediates and transition states by intramolecular hydrogen bonds but also act as a proton donor so that the η(1)-CH3COO(-) ligand could be protonated to form a neutral acetic acid for easy removal. These findings explain why only the methyl hydrogen benzylphosphonates and methyl hydrogen phenylphosphates were found to be suitable reaction partners. Our mechanistic findings are further supported by theoretical prediction of Pd-catalyzed ortho-olefination using methyl hydrogen phenylphosphonate, which is verified by experimental observations that the desired product was formed in a moderate yield.

  7. Ammonia inhibition on hydrogen enriched anaerobic digestion of manure under mesophilic and thermophilic conditions

    DEFF Research Database (Denmark)

    Wang, Han; Zhang, Yifeng; Angelidaki, Irini

    2016-01-01

    Capturing of carbon dioxide by hydrogen derived from excess renewable energy (e.g., wind mills) to methane in a microbially catalyzed process offers an attractive technology for biogas production and upgrading. This bioconversion process is catalyzed by hydrogenotrophic methanogens, which are kno...

  8. Selective conversion of synthesis gas into C2-oxygenated products using mixed-metal homogeneous catalysts

    International Nuclear Information System (INIS)

    Whyman, R.

    1986-01-01

    A feature which is a key to any wider utilization of chemistry based on synthesis gas is an understanding of, and more particularly, an ability to control, those factors which determine the selectivity of the C 1 to C 2 transformation during the hydrogenation of carbon monoxide. With the exception of the rhodium-catalyzed conversion of carbon monoxide and hydrogen into ethylene glycol and methanol, in which molar ethylene glycol/methanol selectivities of ca 2/1 may be achieved, other catalyst systems containing metals such as cobalt or ruthenium exhibit only poor selectivities to ethylene glycol. The initial studies in this area were based on the reasoning that, since the reduction of carbon monoxide to C 2 products is a complex, multi-step process, the use of appropriate combinations of metals could generate synergistic effects which might prove more effective (in terms of both catalytic activity and selectivity) than simply the sum of the individual metal components. In particular, the concept of the combination of a good hydrogenation catalyst with a good carbonylation, or ''CO insertion'', catalyst seemed particularly germane. As a result of this approach the authors discovered an unprecedented example of the effect of catalyst promoters, particularly in the enhancement of C 2 /C 1 selectivity, and one which has led to the development of composite mixed-metal homogeneous catalyst systems for the conversion of CO/H 2 into C 2 -oxygenate esters

  9. Butterfly valve with metal seals controls flow of hydrogen from cryogenic through high temperatures

    Science.gov (United States)

    Johnson, L. D.

    1967-01-01

    Butterfly valve with metal seals operates over a temperature range of minus 423 degrees to plus 440 degrees F with hydrogen as a medium and in a radiation environment. Media flow is controlled by an internal butterfly disk which is rotated by an actuation shaft.

  10. Novel developments in hydrogen storage, hydrogen activation and ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Doroodian, Amir

    2010-12-03

    This dissertation is divided into three chapters. Recently, metal-free hydrogen activation using phosphorous compounds has been reported in science magazine. We have investigated the interaction between hydrogen and phosphorous compounds in presence of strong Lewis acids (chapter one). A new generation of metal-free hydrogen activation, using amines and strong Lewis acids with sterically demanding nature, was already developed in our group. Shortage of high storage capacity using large substitution to improve sterical effect led us to explore the amine borane derivatives, which are explained in chapter two. Due to the high storage capacity of hydrogen in aminoborane derivatives, we have explored these materials to extend hydrogen release. These compounds store hydrogen as proton and hydride on adjacent atoms or ions. These investigations resulted in developing hydrogen storage based on ionic liquids containing methyl guanidinium cation. Then we have continued to develop ionic liquids based on methyl guanidinium cation with different anions, such as tetrafluoro borate (chapter three). We have replaced these anions with transition metal anions to investigate hydrogen bonding and catalytic activity of ionic liquids. This chapter illustrates the world of ionic liquid as a green solvent for organic, inorganic and catalytic reactions and combines the concept of catalysts and solvents based on ionic liquids. The catalytic activity is investigated particularly with respect to the interaction with CO{sub 2}. (orig.)

  11. Carbon material for hydrogen storage

    Science.gov (United States)

    Bourlinos, Athanasios; Steriotis, Theodore; Stubos, Athanasios; Miller, Michael A

    2016-09-13

    The present invention relates to carbon based materials that are employed for hydrogen storage applications. The material may be described as the pyrolysis product of a molecular precursor such as a cyclic quinone compound. The pyrolysis product may then be combined with selected transition metal atoms which may be in nanoparticulate form, where the metals may be dispersed on the material surface. Such product may then provide for the reversible storage of hydrogen. The metallic nanoparticles may also be combined with a second metal as an alloy to further improve hydrogen storage performance.

  12. Effect of preparation method of metal hydride electrode on efficiency of hydrogen electrosorption process

    Energy Technology Data Exchange (ETDEWEB)

    Giza, Krystyna [Czestochowa University of Technology (Poland). Faculty of Production Engineering and Materials Technology; Drulis, Henryk [Trzebiatowski Institute of Low Temperatures and Structure Research PAS, Wroclaw (Poland)

    2016-02-15

    The preparation of negative electrodes for nickel-metal hydride batteries using LaNi{sub 4.3}Co{sub 0.4}Al{sub 0.3} alloy is presented. The constant current discharge technique is employed to determine the discharge capacity, the exchange current density and the hydrogen diffusion coefficient of the studied electrodes. The electrochemical performance of metal hydride electrode is strongly affected by preparation conditions. The results are compared and the advantages and disadvantages of preparation methods of the electrodes are also discussed.

  13. Process for the production of hydrogen from water

    Science.gov (United States)

    Miller, William E [Naperville, IL; Maroni, Victor A [Naperville, IL; Willit, James L [Batavia, IL

    2010-05-25

    A method and device for the production of hydrogen from water and electricity using an active metal alloy. The active metal alloy reacts with water producing hydrogen and a metal hydroxide. The metal hydroxide is consumed, restoring the active metal alloy, by applying a voltage between the active metal alloy and the metal hydroxide. As the process is sustainable, only water and electricity is required to sustain the reaction generating hydrogen.

  14. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura

    2018-04-24

    Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.

  15. Pd(II)-Catalyzed Olefination of sp3 C–H Bonds

    Science.gov (United States)

    Wasa, Masayuki; Engle, Keary M.; Yu, Jin-Quan

    2010-01-01

    The first Pd(II)-catalyzed sp3 C–H olefination reaction has been developed using N-arylamide directing groups. Following olefination, the resulting intermediates were found to undergo rapid 1,4-addition to give the corresponding γ lactams. Notably, this method was effective with substrates containing α-hydrogen atoms and could be applied to effect methylene C–H olefination of cyclopropane substrates. PMID:20187642

  16. Process for exchanging hydrogen isotopes between gaseous hydrogen and water

    International Nuclear Information System (INIS)

    Hindin, S. G.; Roberts, G. W.

    1980-01-01

    A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst

  17. Cellular automaton model for hydrogen transport dynamics through metallic surface

    International Nuclear Information System (INIS)

    Shimura, K.; Yamaguchi, K.; Terai, T.; Yamawaki, M.

    2002-01-01

    Hydrogen re-emission and re-combination at the surface of first wall materials are a crucial issue for the understanding of the fuel recycling and for the tritium inventory in plasma facing materials. It is know to be difficult to model the transient behaviour of those processes due to their complex time-transient nature. However, cellular automata (CA) are powerful tools to model such complex systems because of their nature of discreteness in both dependent and independent variables. Then the system can be represented by the fully local interactions between cells. For that reason, complex physical and chemical systems can be described by fairly simple manner. In this study, the kinetics of desorption of adsorbed hydrogen from an ideal metallic surface is modelled in CA. Thermal desorption is simulated with this model and the comparison with the theory of rate processes is performed to identify the validity of this model. The overall results show that this model is reasonable to express the desorption kinetics

  18. Cleavage of hydrogen by activation at a single non-metal centre - towards new hydrogen storage materials.

    Science.gov (United States)

    Grabowski, Sławomir J

    2015-05-28

    Molecular surfaces of non-metal species are often characterized by both positive and negative regions of electrostatic potential (EP) at a non-metal centre. This centre may activate molecular hydrogen which further leads to the addition reaction. The positive EP regions at the non-metal centres correspond to σ-holes; the latter sites are enhanced by electronegative substituents. This is why the following simple moieties; PFH2, SFH, AsFH2, SeFH, BrF3, PF(CH3)2 and AsF(CH3)2, were chosen here to analyze the H2 activation and its subsequent splitting at the P, As, S, Se and Br centres. Also the reverse H-H bond reforming process is analyzed. MP2/aug-cc-pVTZ calculations were performed for systems corresponding to different stages of these processes. The sulphur centre in the SFH moiety is analyzed in detail since the potential barrier height for the addition reaction for this species is the lowest of the moieties analyzed here. The results of calculations show that the SFH + H2 → SFH3 reaction in the gas phase is endothermic but it is exothermic in polar solvents.

  19. SOLUBILITY OF IRON IN METALLIC HYDROGEN AND STABILITY OF DENSE CORES IN GIANT PLANETS

    International Nuclear Information System (INIS)

    Wahl, Sean M.; Wilson, Hugh F.; Militzer, Burkhard

    2013-01-01

    The formation of the giant planets in our solar system, and likely a majority of giant exoplanets, is most commonly explained by the accretion of nebular hydrogen and helium onto a large core of terrestrial-like composition. The fate of this core has important consequences for the evolution of the interior structure of the planet. It has recently been shown that H 2 O, MgO, and SiO 2 dissolve in liquid metallic hydrogen at high temperature and pressure. In this study, we perform ab initio calculations to study the solubility of an innermost metallic core. We find dissolution of iron to be strongly favored above 2000 K over the entire pressure range (0.4-4 TPa) considered. We compare with and summarize the results for solubilities on other probable core constituents. The calculations imply that giant planet cores are in thermodynamic disequilibrium with surrounding layers, promoting erosion and redistribution of heavy elements. Differences in solubility behavior between iron and rock may influence evolution of interiors, particularly for Saturn-mass planets. Understanding the distribution of iron and other heavy elements in gas giants may be relevant in understanding mass-radius relationships, as well as deviations in transport properties from pure hydrogen-helium mixtures

  20. Hydrogen influence on metals behaviour

    International Nuclear Information System (INIS)

    Tison, P.

    1984-01-01

    Hydrogen isotopes are used in order to investigate the influence of natural oxides and trapping on the permeability of low alloys steels, and martensitic, ferritic, austenitic stainless steels. The permeability of superficial oxides is investigated by reducing and reoxidising the upstream and downstream surfaces (gas ingoing and outgoing faces). The simultaneous or successive use of hydrogen and deuterium enables a direct demonstration of trapping during permeation measurements and a study of the interactions between the diffusing gas and hydrogen absorbed during steel making and processing [fr

  1. Liquid metal purification device

    International Nuclear Information System (INIS)

    Sakai, Takao; Shimoyashiki, Shigehiro.

    1992-01-01

    The device of the present invention concerns a liquid metal purification device for removing and purifying impuries in liquid metal sodium used as coolants of an FBR type reactor. A vessel having a group of pipes made of hydrogen permeable metal at the inside thereof is disposed to the inlet pipeline of a cold trap. The group of hydrogen permeable metal pipes is connected to an exhaust pipe and a vacuum pump, so that the inside of the pipes is exhausted. Liquid metal sodium branched from the main pipeline of a coolant system passes through the outer side of the group of the hydrogen permeable metal pipes. In this cae, hydrogen contained as impurities in the liquid metal sodium diffuses and permeates the hydrogen permeation metal pipes and enters into the pipe group and is discharged out of the system by the vacuum pump. This can mitigate the hydrogen removing burden of the cold trap, to extend the device life time. (I.N.)

  2. Magnesium mechanical alloys for hydrogen storage

    International Nuclear Information System (INIS)

    Ivanov, E.; Konstanchuk, I.; Stepanov, A.; Boldyrev, V.

    1985-01-01

    Metal hybrides are currently being used to store and handle hydrogen and its isotopes. They are also being tested in hydrogen compressors and in heat energy, refrigerators and in hydrogen and thermal storage devices. Metal hydrides have been proposed as one of the possible media for hydrogen storage to overcome the limitations of other techniques in regard to safety hydrogen weight and volume ration. The suitability of metal hybrides as a hydrogen storage media depends on a number of factors such as storage capacity, reactivity with hydrogen at various pressures and temperatures, and the cost of base materials. Magnesium based alloys are promising materials for storing hydrogen. They are generally made by argon melting and no attention has been payed to other fabrication techniques such as mechanical alloying or powder technique

  3. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  4. Hydrogen storage via polyhydride complexes

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, C.M.; Zidan, R.A. [Univ. of Hawaii, Honolulu, HI (United States)

    1998-08-01

    The reversible dehydrogenation of NaAlH{sub 4} is catalyzed in toluene slurries of the NaAlH{sub 4} containing the pincer complex, IrH{sub 4} {l_brace}C{sub 6}H{sub 3}-2,6-(CH{sub 2}PBu{sup t}{sub 2}){sub 2}{r_brace}. The rates of the pincer complex catalyzed dehydrogenation are about five times greater those previously found for NaAlH{sub 4} that was doped with titanium through a wet chemistry method. Homogenization of NaAlH{sub 4} with 2 mole % Ti(OBu{sup n}){sub 4} under an atmosphere of argon produces a novel titanium containing material. TPD measurements show that the dehydrogenation of this material occurs about 30 C lower than that previously found for wet titanium doped NaAlH{sub 4}. In further contrast to wet doped NaAlH{sub 4}, the dehydrogenation kinetics and hydrogen capacity of the novel material are undiminished over several dehydriding/hydriding cycles. Rehydrogenation of the titanium doped material occurs readily at 170 C under 150 atm of hydrogen. TPD measurements show that about 80% of the original hydrogen content (4.2 wt%) can be restored under these conditions.

  5. Development of hydrogen oxidizing bacteria using hydrogen from radiolysis or metal corrosion; Developpement de populations microbiennes oxydant l'hydrogene produit par radiolyse ou par corrosion des metaux

    Energy Technology Data Exchange (ETDEWEB)

    Libert, M F; Sellier, R; Marty, V; Camaro, S [CEA Cadarache, Dept. d' Entreposage et de Stockage des Dechets (DCC/DESD/SEP), 13 - Saint-Paul-lez-Durance (France)

    2000-07-01

    The effect of many parameters need to be studied to characterize the long term behavior of nuclear waste in a deep repository. These parameters concern the chemical effects, radiolytic effects, mechanical properties, water composition, and microbiological activity. To evaluate microbial activity in such an environment, work was focused on an inventory of key nutrients (C, H, 0, N, P, S) and energy sources required for bacterial growth. The production of hydrogen in the nuclear waste environment leads to the growth of hydrogen oxidizing bacteria, which modify the gas production balance. A deep repository containing bituminized waste drums implies several sources of hydrogen: - water radiolysis; -corrosion of metal containers; - radiolysis of the embedding matrix (bitumen). Two deep geological disposal conditions leading to H{sub 2} production in a bituminized nuclear waste environment were simulated in the present study: - H{sub 2} production by iron corrosion under anaerobic conditions was simulated by adding 10% of H{sub 2} in the atmosphere; - H{sub 2} production by radiolysis of bitumen matrix was approached by subjecting this material to external gamma irradiation with a dose rate near real conditions (6 Gy/h). The presence of dissolved H{sub 2} in water allows the growth of hydrogen oxidizing bacteria leading to: - CO{sub 2} and N{sub 2} production; - H{sub 2} consumption; - lower NO{sub 3}{sup -} concentration caused by reduction to nitrogen. In the first case, hydrogen consumption is limited by the NO{sub 3}{sup -} release rate from the bitumen matrix. In the second case, however, under gamma radiation at a low dose rate, hydrogen production is weak, and the hydrogen is completely consumed by microorganisms. Knowledge about these hydrogen oxidizing bacteria is just beginning to emerge. Heterotrophic denitrifying bacteria adapt well to hydrogen metabolism (autotrophic metabolism) by oxidizing H{sub 2} instead of hydrocarbons. (authors)

  6. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong; Li, Wengang; Yan, Jingjing; Moosa, Basem; Amad, Maan H.; Werth, Charles; Khashab, Niveen M.

    2012-01-01

    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong

    2012-09-27

    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Achievement report for 1st phase (fiscal 1974-80) Sunshine Program research and development - Hydrogen energy. Research on transportation of hydrogen in the form of metallic hydride; 1974-1980 nendo kinzoku suisokabutsu ni yoru suiso no yuso gijutsu no kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-03-01

    This report concerns the transportation and storage of hydrogen using metallic hydrides that perform absorption and desorption of hydrogen. Alloys useable for this purpose have to be capable of reversibly absorbing and desorbing hydrogen within a certain temperature range. In the absence of guidelines to follow in the quest for such alloys, the efforts at discovering them turned out to be a continual series of trials and errors. Researches were conducted into the hydrogenation reaction of Mg and Mg-based alloys and into hydrides of V-based alloys, and into Zr-based alloy hydrides such as the ZrMn{sub 2} hydride, ZrNiMn hydride, Zr(Fe{sub x}Mn{sub 1-x}){sub 2} hydrides, TiZrFe{sub 2} hydride, Zr{sub x}Ti{sub 1-x}(Fe{sub y}Mn{sub 1-y}) hydrides, etc. Also studied were the electronics of hydrogen in metallic hydrides, rates of reaction between Mg-Ni-based alloys and hydrogen systems, endurance tests for hydrides of Mg-Ni-based alloys, effects exerted by absorbed gas molecules during the storage of hydrogen in Mg-Ni-based alloys, effective thermal conductivity in a layer filled with a metallic hydride, metallic hydride-aided hydrogen transportation systems, chemical boosters, etc. (NEDO)

  9. Hydrogen Absorption in Metal Thin Films and Heterostructures Investigated in Situ with Neutron and X-ray Scattering

    Directory of Open Access Journals (Sweden)

    Sara J. Callori

    2016-05-01

    Full Text Available Due to hydrogen possessing a relatively large neutron scattering length, hydrogen absorption and desorption behaviors in metal thin films can straightforwardly be investigated by neutron reflectometry. However, to further elucidate the chemical structure of the hydrogen absorbing materials, complementary techniques such as high resolution X-ray reflectometry and diffraction remain important too. Examples of work on such systems include Nb- and Pd-based multilayers, where Nb and Pd both have strong affinity to hydrogen. W/Nb and Fe/Nb multilayers were measured in situ with unpolarized and polarized neutron reflectometry under hydrogen gas charging conditions. The gas-pressure/hydrogen-concentration dependence, the hydrogen-induced macroscopic film swelling as well as the increase in crystal lattice plane distances of the films were determined. Ferromagnetic-Co/Pd multilayers were studied with polarized neutron reflectometry and in situ ferromagnetic resonance measurements to understand the effect of hydrogen absorption on the magnetic properties of the system. This electronic effect enables a novel approach for hydrogen sensing using a magnetic readout scheme.

  10. High performance hydrogen storage from Be-BTB metal-organic framework at room temperature.

    Science.gov (United States)

    Lim, Wei-Xian; Thornton, Aaron W; Hill, Anita J; Cox, Barry J; Hill, James M; Hill, Matthew R

    2013-07-09

    The metal-organic framework beryllium benzene tribenzoate (Be-BTB) has recently been reported to have one of the highest gravimetric hydrogen uptakes at room temperature. Storage at room temperature is one of the key requirements for the practical viability of hydrogen-powered vehicles. Be-BTB has an exceptional 298 K storage capacity of 2.3 wt % hydrogen. This result is surprising given that the low adsorption enthalpy of 5.5 kJ mol(-1). In this work, a combination of atomistic simulation and continuum modeling reveals that the beryllium rings contribute strongly to the hydrogen interaction with the framework. These simulations are extended with a thermodynamic energy optimization (TEO) model to compare the performance of Be-BTB to a compressed H2 tank and benchmark materials MOF-5 and MOF-177 in a MOF-based fuel cell. Our investigation shows that none of the MOF-filled tanks satisfy the United States Department of Energy (DOE) storage targets within the required operating temperatures and pressures. However, the Be-BTB tank delivers the most energy per volume and mass compared to the other material-based storage tanks. The pore size and the framework mass are shown to be contributing factors responsible for the superior room temperature hydrogen adsorption of Be-BTB.

  11. 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.

  12. The creation of strongly coupled plasmas using an intense heavy ion beam: low-entropy compression of hydrogen and the problem of hydrogen metallization

    Energy Technology Data Exchange (ETDEWEB)

    Tahir, N A [Institut fuer Theoretische Physik, Universitaet Frankfurt, Postfach 11 19 32, 60054 Frankfurt (Germany); Piriz, A R [ETSI Industriales, Universidad de Castilla-La Mancha, 13071 Ciudad Real (Spain); Shutov, A [Institute for Problems in Chemical Physics Research, Chernogolovka, Russia (Russian Federation); Varentsov, D [Institut fuer Kernphysik, Technische Universitaet Darmstadt, Schlossgarten Str. 9, 64289 Darmstadt (Germany); Udrea, S [Institut fuer Kernphysik, Technische Universitaet Darmstadt, Schlossgarten Str. 9, 64289 Darmstadt (Germany); Hoffmann, D H H [Institut fuer Kernphysik, Technische Universitaet Darmstadt, Schlossgarten Str. 9, 64289 Darmstadt (Germany); Juranek, H [Fachbereich Physik, Universitaet Rostock, 18051 Rostock (Germany); Redmer, R [Fachbereich Physik, Universitaet Rostock, 18051 Rostock (Germany); Portugues, R F [ETSI Industriales, Universidad de Castilla-La Mancha, 13071 Ciudad Real (Spain); Lomonosov, I [Institute for Problems in Chemical Physics Research, Chernogolovka, Russia (Russian Federation); Fortov, V E [Institute for Problems in Chemical Physics Research, Chernogolovka, Russia (Russian Federation)

    2003-06-06

    Intense heavy ion beams deposit energy very efficiently over extended volumes of solid density targets, thereby creating large samples of strongly coupled plasmas. Intense beams of energetic heavy ions are therefore an ideal tool to research this interesting field. It is also possible to design experiments using special beam-target geometries to achieve low-entropy compression of samples of matter. This type of experiments is of particular interest for studying the problem of hydrogen metallization. In this paper we present a design study of such a proposed experiment that will be carried out at the future heavy ion synchrotron facility SIS100, at the Gesellschaft fuer Schwerionenforschung, Darmstadt. This study has been done using a two-dimensional hydrodynamic computer code. The target consists of a solid hydrogen cylinder that is enclosed in a thick shell of lead whose one face is irradiated with an ion beam which has an annular (ring shaped) focal spot. The beam intensity and other parameters are considered to be the same as expected at the future SIS100 facility. The simulations show that due to multiple shock reflection between the cylinder axis and the lead-hydrogen boundary, one can achieve up to 20 times solid density in hydrogen while keeping the temperature as low as a few thousand K. The corresponding pressure is of the order of 10 Mbar. These values of the physical parameters lie within the range of theoretically predicted values for hydrogen metallization. We have also carried out a parameter study of this problem by varying the target and beam parameters over a wide range. It has been found that the results are very insensitive to such changes in the input parameters.

  13. The creation of strongly coupled plasmas using an intense heavy ion beam: low-entropy compression of hydrogen and the problem of hydrogen metallization

    International Nuclear Information System (INIS)

    Tahir, N A; Piriz, A R; Shutov, A; Varentsov, D; Udrea, S; Hoffmann, D H H; Juranek, H; Redmer, R; Portugues, R F; Lomonosov, I; Fortov, V E

    2003-01-01

    Intense heavy ion beams deposit energy very efficiently over extended volumes of solid density targets, thereby creating large samples of strongly coupled plasmas. Intense beams of energetic heavy ions are therefore an ideal tool to research this interesting field. It is also possible to design experiments using special beam-target geometries to achieve low-entropy compression of samples of matter. This type of experiments is of particular interest for studying the problem of hydrogen metallization. In this paper we present a design study of such a proposed experiment that will be carried out at the future heavy ion synchrotron facility SIS100, at the Gesellschaft fuer Schwerionenforschung, Darmstadt. This study has been done using a two-dimensional hydrodynamic computer code. The target consists of a solid hydrogen cylinder that is enclosed in a thick shell of lead whose one face is irradiated with an ion beam which has an annular (ring shaped) focal spot. The beam intensity and other parameters are considered to be the same as expected at the future SIS100 facility. The simulations show that due to multiple shock reflection between the cylinder axis and the lead-hydrogen boundary, one can achieve up to 20 times solid density in hydrogen while keeping the temperature as low as a few thousand K. The corresponding pressure is of the order of 10 Mbar. These values of the physical parameters lie within the range of theoretically predicted values for hydrogen metallization. We have also carried out a parameter study of this problem by varying the target and beam parameters over a wide range. It has been found that the results are very insensitive to such changes in the input parameters

  14. Influence of metal doping of a MOF-74 framework on hydrogen adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Botas, J.A.; Calleja, G.; Orcajo, M.G. [Rey Juan Carlos Univ., Madrid (Spain). Dept. of Chemical and Energy Technology; Sanchez-Sanchez, M. [CSIC, Madrid (Spain). Inst. de Catalisis y Petroleoquimica

    2010-07-01

    Microporous Metal-Organic Framework (MOF) adsorbents are considered an interesting option for hydrogen storage. Due to their porous nature and unusually high surface areas, these materials show an exceptional H{sub 2} uptake. Unfortunately, their interaction with H{sub 2} molecules is weak, so cryogenic temperatures are required to reach competitive H{sub 2} storage capacities. In this sense, the presence of coordinatively unsaturated and exposed metal centers in some MOF frameworks could increase the affinity for H{sub 2} through stronger metal-H{sub 2} interactions. In this preliminary work, the effect of doping a Zn{sup 2+}-MOF-74 framework with Co{sup 2+}, Cu{sup 2+} and Mg{sup 2+} on its adsorption properties for H{sub 2} has been studied. Characterization studies suggest that the samples prepared have actually the MOF-74 structure, in which the different tested heteroatom ions have been successfully incorporated. The differences in H{sub 2} adsorption at 77 K and 87 K between the MOF-74 samples doped with the mentioned divalent metal ions were discussed as a function of their free pore volume and amount of metal incorporation. (orig.)

  15. Effects of metal salt catalysts on yeast cell growth in ethanol conversion

    Science.gov (United States)

    Chung-Yun Hse; Yin Lin

    2009-01-01

    The effects of the addition of metal salts and metal salt-catalyzed hydrolyzates on yeast cell growth in ethanol fermentation were investigated. Four yeast strains (Saccharomyces cerevisiae WT1, Saccharomyces cerevisiae MT81, Candida sp. 1779, and Klumaromyces fragilis), four metal salts (CuCl2, FeCl3, AgNO3, and I2), two metal salt-catalyzed hydrolyzates (...

  16. Metal hydride electrode and nickel hydrogen storage battery; Suiso kyuzo gokin denkyoku oyobi nikkeru-suiso chikudenchi

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Y.; Tamagawa, H. [Shin-Kobe Electric Machinery Co. Ltd., Tokyo (Japan); Ikawa, A.; Muranaka, R. [Hitachi Ltd., Ibaraki (Japan). Hitachi Research Lab.

    1996-04-16

    Water soluble polymers such as cellulose derivatives and polyvinylalcohol have been used conventionally as binders for metal hydride electrode used for nickel-hydrogen storage batteries. The shortcomings of those binders, however, are low flexibility, and poor binding property for hydrogen absorbing alloy powder and the conductive supporting substrate. This invention relates to the use of ethylene-vinyl copolymer with less than -10{degree}C Tg as the binder for hydrogen absorbing alloy powder. It is desirable that the ethylene-vinylacetate copolymer is selected out of ethylene-vinyl acetate-acryl copolymer and ethylene-vinyl acetate-long chain vinyl ester copolymer, and that the addition is larger than 0.1wt% and less than 1wt% against the weight of hydrogen absorbing alloy in the electrode. The use of this binder results in strong binding of hydrogen absorbing alloy powder to the conductive supporting substrate, providing flexibility as well. 4 figs., 5 tabs.

  17. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.; Ravishankar, T.N.; Ramakrishnappa, T.; Nagaraju, Doddahalli H.; Krishna Pai, Ranjith

    2015-01-01

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic

  18. Reversible Interconversion between 2,5-Dimethylpyrazine and 2,5-Dimethylpiperazine by Iridium-Catalyzed Hydrogenation/Dehydrogenation for Efficient Hydrogen Storage.

    Science.gov (United States)

    Fujita, Ken-Ichi; Wada, Tomokatsu; Shiraishi, Takumi

    2017-08-28

    A new hydrogen storage system based on the hydrogenation and dehydrogenation of nitrogen heterocyclic compounds, employing a single iridium catalyst, has been developed. Efficient hydrogen storage using relatively small amounts of solvent compared with previous systems was achieved by this new system. Reversible transformations between 2,5-dimethylpyrazine and 2,5-dimethylpiperazine, accompanied by the uptake and release of three equivalents of hydrogen, could be repeated almost quantitatively at least four times without any loss of efficiency. Furthermore, hydrogen storage under solvent-free conditions was also accomplished. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  20. Influence of bulk and surface phenomena on the hydrogen permeation through metals

    International Nuclear Information System (INIS)

    Waelbroeck, F.; Wienhold, P.; Winter, J.; Rota, E.; Bauno, T.

    1984-12-01

    We discuss the permeation of hydrogen through metals and alloys such as iron, nickel, steels and Inconel wherein H dissolves endothermically from an H 2 gas. We assume first that trapping centers, surface contamination layers, the saturation of the H surface coverage and the implantation profile - when energetic ions drive the permeation - can be neglected, that a quasi-equilibrium exists between the H atom concentration ν in the adsorbed layer and c in the near surface layers and that the H solubility and diffusivity are homogeneous in the membrane. We evaluate thereafter separately the influence of these various effects and identify the parameter domains where appreciable corrections result. The permeation phenomenon is complex even when these simplifications are made: the penetration rate is proportional to the flux of thermal molecules, atoms or energetic ions - depending upon the case - which strike the surface; the diffusion in the metal is proportional to the gradient of c; the release rate depends on c 2 ; the time-dependent diffusion equation includes a double spatial derivative of c. Permeation can only be fully described when computer codes such as PERI is used. Simple analytical relations are however obtained in several limiting cases. They are the object of this report. Some of them had already been derived by other authors but they were not shown to be part of a single, self consistent permeation model. A comparison of predicted and experimental results shows that the simplified model describes surprisingly accurately the hydrogen exchange between gas and metal solutions. (orig./GSCH)

  1. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  2. Hydrogen peroxide as a sustainable energy carrier: Electrocatalytic production of hydrogen peroxide and the fuel cell

    International Nuclear Information System (INIS)

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D.

    2012-01-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal–oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

  3. Advancement of Systems Designs and Key Engineering Technologies for Materials Based Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    van Hassel, Bart A. [United Technologies Research Center, East Hartford, CT (United States)

    2015-09-18

    UTRC lead the development of the Simulink Framework model that enables a comparison of different hydrogen storage systems on a common basis. The Simulink Framework model was disseminated on the www.HSECoE.org website that is hosted by NREL. UTRC contributed to a better understanding of the safety aspects of the proposed hydrogen storage systems. UTRC also participated in the Failure Mode and Effect Analysis of both the chemical- and the adsorbent-based hydrogen storage system during Phase 2 of the Hydrogen Storage Engineering Center of Excellence. UTRC designed a hydrogen storage system with a reversible metal hydride material in a compacted form for light-duty vehicles with a 5.6 kg H2 storage capacity, giving it a 300 miles range. It contains a heat exchanger that enables efficient cooling of the metal hydride material during hydrogen absorption in order to meet the 3.3 minute refueling time target. It has been shown through computation that the kinetics of hydrogen absorption of Ti-catalyzed NaAlH4 was ultimately limiting the rate of hydrogen absorption to 85% of the material capacity in 3.3 minutes. An inverse analysis was performed in order to determine the material property requirements in order for a metal hydride based hydrogen storage system to meet the DOE targets. Work on metal hydride storage systems was halted after the Phase 1 to Phase 2 review due to the lack of metal hydride materials with the required material properties. UTRC contributed to the design of a chemical hydrogen storage system by developing an adsorbent for removing the impurity ammonia from the hydrogen gas, by developing a system to meter the transport of Ammonia Borane (AB) powder to a thermolysis reactor, and by developing a gas-liquid-separator (GLS) for the separation of hydrogen gas from AB slurry in silicone oil. Stripping impurities from hydrogen gas is essential for a long life of the fuel cell system on board of a vehicle. Work on solid transport of AB was halted after the

  4. The Liquid Metallic Hydrogen Model of the Sun and the Solar Atmosphere VII. Further Insights into the Chromosphere and Corona

    Directory of Open Access Journals (Sweden)

    Robitaille P.-M.

    2013-07-01

    Full Text Available In the liquid metallic hydrogen model of the Sun, the chromosphere is responsible for the capture of atomic hydrogen in the solar atmosphere and its eventual re-entry onto the photospheric surface (P.M. Robitaille. The Liquid Metallic Hydrogen Model of the Sun and the Solar Atmosphere IV. On the Nature of the Chromosphere. Prog. Phys., 2013, v. 3, L15–L21. As for the corona, it represents a diffuse region containing both gaseous plasma and condensed matter with elevated electron affinity (P.M. Robitaille. The Liquid Metallic Hydrogen Model of the Sun and the Solar Atmosphere V. On the Nature of the Corona. Prog. Phys., 2013, v. 3, L22–L25. Metallic hydrogen in the corona is thought to enable the continual harvest of electrons from the outer reaches of the Sun, thereby preserving the neutrality of the solar body. The rigid rotation of the corona is offered as the thirty-third line of evidence that the Sun is comprised of condensed matter. Within the context of the gaseous models of the Sun, a 100 km thick transition zone has been hypothesized to exist wherein temperatures increase dramatically from 104–106 K. Such extreme transitional temperatures are not reasonable given the trivial physical scale of the proposed transition zone, a region adopted to account for the ultra-violet emission lines of ions such as C IV, O IV, and Si IV. In this work, it will be argued that the transition zone does not exist. Rather, the intermediate ionization states observed in the solar atmosphere should be viewed as the result of the simultaneous transfer of protons and electrons onto condensed hydrogen structures, CHS. Line emissions from ions such as C IV, O IV, and Si IV are likely to be the result of condensation reactions, manifesting the involvement of species such as CH4, SiH4, H3O+ in the synthesis of CHS in the chromosphere. In addition, given the presence of a true solar surface at the level of the photosphere in the liquid metallic hydrogen model

  5. Enhanced Electrochemical Hydrogen Storage Performance on the Porous Graphene Network Immobilizing Cobalt Metal Nanoparticle

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Myunggoo; Lee, Dong Heon; Jung, Hyun [Dongguk University, Seoul (Korea, Republic of)

    2016-05-15

    In this study, we attempted to apply Co metal nanoparticles decorated on the surface of the porous graphene (Co-PG) as the electrochemical hydrogen storage system. Co-PG was successfully synthesized by the soft-template method. To determine the synthetic strategy of porous graphene and Co nanoparticles, we compare the obtained Co-PG with two different materials such as Co nanoparticle decorated reduced graphene oxide without soft-template (Co-RGO) and porous graphene without Co nanoparticle (PG). The experimental details regarding the synthesis and characterization of the Co-PG, Co-RGO, and PG samples are provided in Supporting Information. Co-PG with interpenetrating porous networks and immobilized Co metal nanoparticles were successfully synthesized by the soft-template method. The obtained Co-PG exhibited high-surface area with ink-bottle open pores owing to the homogeneous dispersion of P123 micellar rods. The XRD and FE-SEM analyses clearly confirm that Co nanoparticles were immobilized on to the surface of porous graphene without any significant aggregation. The as-obtained Co-PG showed good electrochemical performance such as capacity and cycle stability for hydrogen storage. Based on these results, we believe that the Co-PG with a high-specific surface area could be worthwhile to investigate as not only electrochemical hydrogen storage materials but also other energy storage applications.

  6. Enhanced Electrochemical Hydrogen Storage Performance on the Porous Graphene Network Immobilizing Cobalt Metal Nanoparticle

    International Nuclear Information System (INIS)

    Kang, Myunggoo; Lee, Dong Heon; Jung, Hyun

    2016-01-01

    In this study, we attempted to apply Co metal nanoparticles decorated on the surface of the porous graphene (Co-PG) as the electrochemical hydrogen storage system. Co-PG was successfully synthesized by the soft-template method. To determine the synthetic strategy of porous graphene and Co nanoparticles, we compare the obtained Co-PG with two different materials such as Co nanoparticle decorated reduced graphene oxide without soft-template (Co-RGO) and porous graphene without Co nanoparticle (PG). The experimental details regarding the synthesis and characterization of the Co-PG, Co-RGO, and PG samples are provided in Supporting Information. Co-PG with interpenetrating porous networks and immobilized Co metal nanoparticles were successfully synthesized by the soft-template method. The obtained Co-PG exhibited high-surface area with ink-bottle open pores owing to the homogeneous dispersion of P123 micellar rods. The XRD and FE-SEM analyses clearly confirm that Co nanoparticles were immobilized on to the surface of porous graphene without any significant aggregation. The as-obtained Co-PG showed good electrochemical performance such as capacity and cycle stability for hydrogen storage. Based on these results, we believe that the Co-PG with a high-specific surface area could be worthwhile to investigate as not only electrochemical hydrogen storage materials but also other energy storage applications

  7. 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.

  8. 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

  9. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    International Nuclear Information System (INIS)

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

    2011-01-01

    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

  10. Hydrogen environment embrittlement

    International Nuclear Information System (INIS)

    Donovan, J.A.

    1975-01-01

    Exposure of many metals to gaseous hydrogen causes losses in elongation, reduction of area, and fracture toughness, and causes increases in slow crack growth rate or fatigue life compared with values obtained in air or vacuum. Hydrogen pressure, temperature, and purity significantly influence deleterious effects. The strength and structural characteristics of the metal influence the degradation of its properties by hydrogen. Several theories have been proposed to explain the loss of properties in hydrogen, but none has gained wide acceptance. The embrittlement mechanism and the role of diffusion are, therefore, open questions and need more quantitative experimental data both to test the proposed theories and to allow the development of realistic preventive measures. (U.S.)

  11. Metal (Ag/Ti)-Containing Hydrogenated Amorphous Carbon Nanocomposite Films with Enhanced Nanoscratch Resistance: Hybrid PECVD/PVD System and Microstructural Characteristics.

    Science.gov (United States)

    Constantinou, Marios; Nikolaou, Petros; Koutsokeras, Loukas; Avgeropoulos, Apostolos; Moschovas, Dimitrios; Varotsis, Constantinos; Patsalas, Panos; Kelires, Pantelis; Constantinides, Georgios

    2018-03-30

    This study aimed to develop hydrogenated amorphous carbon thin films with embedded metallic nanoparticles (a-C:H:Me) of controlled size and concentration. Towards this end, a novel hybrid deposition system is presented that uses a combination of Plasma Enhanced Chemical Vapor Deposition (PECVD) and Physical Vapor Deposition (PVD) technologies. The a-C:H matrix was deposited through the acceleration of carbon ions generated through a radio-frequency (RF) plasma source by cracking methane, whereas metallic nanoparticles were generated and deposited using terminated gas condensation (TGC) technology. The resulting material was a hydrogenated amorphous carbon film with controlled physical properties and evenly dispersed metallic nanoparticles (here Ag or Ti). The physical, chemical, morphological and mechanical characteristics of the films were investigated through X-ray reflectivity (XRR), Raman spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM) and nanoscratch testing. The resulting amorphous carbon metal nanocomposite films (a-C:H:Ag and a-C:H:Ti) exhibited enhanced nanoscratch resistance (up to +50%) and low values of friction coefficient (<0.05), properties desirable for protective coatings and/or solid lubricant applications. The ability to form nanocomposite structures with tunable coating performance by potentially controlling the carbon bonding, hydrogen content, and the type/size/percent of metallic nanoparticles opens new avenues for a broad range of applications in which mechanical, physical, biological and/or combinatorial properties are required.

  12. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    Science.gov (United States)

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Hydrogen transport behavior of metal coatings for plasma-facing components

    Energy Technology Data Exchange (ETDEWEB)

    Anderl, R.A.; Holland, D.F.; Longhurst, G.R. (Idaho National Engineering Lab., Idaho Falls (USA))

    1990-12-01

    Plasma-facing components for experimental and commercial fusion reactor studies may include cladding or coatings of refractory metals like tungsten on metallic structural substrates such as copper, vanadium alloys and austenitic stainless steel. Issues of safety and fuel economy include the potential for inventory buildup and permeation of tritium implanted into the plasma-facing surface. This paper reports on laboratory-scale studies with 3 keV D{sub 3}{sup +} ion beams to investigate the hydrogen transport behavior in tungsten coatings on substrates of copper. These experiments entailed measurements of the deuterium re-emission and permeation rates of tungsten, copper, and tungsten-coated copper specimens at temperatures ranging from 638 to 825 K and implanting particle fluxes of approximately 5x10{sup 19} D/m{sup 2} s. Diffusion constants and surface recombination coefficients with enhancement factors due to sputtering were obtained from these measurements. These data may be used in calculations to estimate permeation rates and inventory buildups for proposed diverter designs. (orig.).

  14. Hydrogen transport behavior of metal coatings for plasma-facing components

    Science.gov (United States)

    Anderl, R. A.; Holland, D. F.; Longhurst, G. R.

    1990-12-01

    Plasma-facing components for experimental and commercial fusion reactor studies may include cladding or coatings of refractory metals like tungsten on metallic structural substrates such as copper, vanadium alloys and austenitic stainless steel. Issues of safety and fuel economy include the potential for inventory buildup and permeation of tritium implanted into the plasma-facing surface. This paper reports on laboratory-scale studies with 3 keV D +3 ion beams to investigate the hydrogen transport behavior in tungsten coatings on substrates of copper. These experiments entailed measurements of the deuterium re-emission and permeation rates for tungsten, copper, and tungsten-coated copper specimens at temperatures ranging from 638 to 825 K and implanting particle fluxes of approximately 5 × 10 19 D/m 2 s. Diffusion constants and surface recombination coefficients with enhancement factors due to sputtering were obtained from these measurements. These data may be used in calculations to estimate permeation rates and inventory buildups for proposed diverter designs.

  15. Hydrogen transport behavior of metal coatings for plasma facing components

    International Nuclear Information System (INIS)

    Anderl, R.A.; Holland, D.F.; Longhurst, G.R.

    1990-01-01

    Plasma-facing components for experimental and commercial fusion reactor studies may include cladding or coatings of refractory metals like tungsten on metallic structural substrates such as copper, vanadium alloys and austenitic stainless steel. Issues of safety and fuel economy include the potential for inventory buildup and permeation of tritium implanted into the plasma-facing surface. This paper reports on laboratory-scale studies with 3-keV D 3 + ion beams to investigate the hydrogen transport behavior in tungsten coatings on substrates of copper. These experiments entailed measurements of the deuterium re-emission and permeation rates for tungsten, copper, and tungsten-coated copper specimens at temperatures ranging from 638 K to 825 K and implanting particle fluxes of approximately 5 x 10 19 D/m 2 s. Diffusion constants and surface recombination coefficients with enhancement factors due to sputtering were obtained from these measurements. These data may be used in calculations to estimate permeation rates and inventory buildups for proposed diverter designs. 18 refs., 3 figs., 3 tabs

  16. Photochemically engineering the metal-semiconductor interface for room-temperature transfer hydrogenation of nitroarenes with formic acid.

    Science.gov (United States)

    Li, Xin-Hao; Cai, Yi-Yu; Gong, Ling-Hong; Fu, Wei; Wang, Kai-Xue; Bao, Hong-Liang; Wei, Xiao; Chen, Jie-Sheng

    2014-12-08

    A mild photochemical approach was applied to construct highly coupled metal-semiconductor dyads, which were found to efficiently facilitate the hydrogenation of nitrobenzene. Aniline was produced in excellent yield (>99 %, TOF: 1183) using formic acid as hydrogen source and water as solvent at room temperature. This general and green catalytic process is applicable to a wide range of nitroarenes without the involvement of high-pressure gases or sacrificial additives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Cheneviere, Yohan; Caps, Valerie; Tuel, Alain

    2010-01-01

    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

  18. A DFT investigation on group 8B transition metal-doped silicon carbide nanotubes for hydrogen storage application

    Science.gov (United States)

    Tabtimsai, Chanukorn; Ruangpornvisuti, Vithaya; Tontapha, Sarawut; Wanno, Banchob

    2018-05-01

    The binding of group 8B transition metal (TMs) on silicon carbide nanotubes (SiCNT) hydrogenated edges and the adsorption of hydrogen molecule on the pristine and TM-doped SiCNTs were investigated using the density functional theory method. The B3LYP/LanL2DZ method was employed in all calculations for the considered structural, adsorption, and electronic properties. The Os atom doping on the SiCNT is found to be the strongest binding. The hydrogen molecule displays a weak interaction with pristine SiCNT, whereas it has a strong interaction with TM-doped SiCNTs in which the Os-doped SiCNT shows the strongest interaction with the hydrogen molecule. The improvement in the adsorption abilities of hydrogen molecule onto TM-doped SiCNTs is due to the protruding structure and the induced charge transfer between TM-doped SiCNT and hydrogen molecule. These observations point out that TM-doped SiCNTs are highly sensitive toward hydrogen molecule. Moreover, the adsorptions of 2-5 hydrogen molecules on TM-doped SiCNT were also investigated. The maximum storage number of hydrogen molecules adsorbed on the first layer of TM-doped SiCNTs is 3 hydrogen molecules. Therefore, TM-doped SiCNTs are suitable to be sensing and storage materials for hydrogen gas.

  19. Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

    2018-05-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

  20. Hydrogen production from biomass by biological systems

    International Nuclear Information System (INIS)

    Sharifan, H.R.; Qader, S.

    2009-01-01

    Hydrogen gas is seen as a future energy carrier, not involved in 'greenhouse' gas and its released energy in combustion can be converted to electric power. Biological system with low energy can produce hydrogen compared to electrochemical hydrogen production via solar battery-based water splitting which requires the use of solar batteries with high energy requirements. The biological hydrogen production occurs in microalgae and cyanobacteria by photosynthesis. They consume biochemical energy to produce molecular hydrogen. Hydrogen in some algae is an anaerobic production in the absence of light. In cyanobacteria the hydrogen production simultaneously happens with nitrogen fixation, and also catalyzed by nitrogenase as a side reaction. Hydrogen production by photosynthetic bacteria is mediated by nitrogenase activity, although hydrogenases may be active for both hydrogen production and hydrogen uptake under some conditions. Genetic studies on photosynthetic microorganisms have markedly increased in recent times, relatively few genetic engineering studies have focused on altering the characteristics of these microorganisms, particularly with respect to enhancing the hydrogen-producing capabilities of photosynthetic bacteria and cyanobacteria. (author)

  1. Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor

    Science.gov (United States)

    Dhooge, Patrick M.

    1987-10-13

    A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.

  2. Time-Dependent Density Functional Theory Analysis of Triphenylamine-Functionalized Graphene Doped with Transition Metals for Photocatalytic Hydrogen Production.

    Science.gov (United States)

    Mota, Elder A V; Neto, Abel F G; Marques, Francisco C; Mota, Gunar V S; Martins, Marcelo G; Costa, Fabio L P; Borges, Rosivaldo S; Neto, Antonio M J C

    2018-07-01

    The electronic structures and optical properties of triphenylamine-functionalized graphene (G-TPA) doped with transition metals, using water as a solvent, were theoretically investigated to verify the efficiency of photocatalytic hydrogen production with the use of transition metals. This study was performed by Density Functional Theory and Time-dependent Density Functional Theory through Gaussian 09W software, adopting the B3LYP functional for all structures. The 6-31g(d) basis set was used for H, C and N atoms, and the LANL2DZ basis set for transition metals using the Effective Core Potentials method. Two approaches were adopted: (1) using single metallic dopants (Ni, Pd, Fe, Os and Pt) and (2) using combinations of Ni with the other dopants (NiPd, NiPt, NiFe and NiOs). The DOS spectra reveal an increase of accessible states in the valence shell, in addition to a gap decrease for all dopants. This doping also increases the absorption in the visible region of solar radiation where sunlight is most intense (400 nm to 700 nm), with additional absorption peaks. The results lead us to propose the G-TPA structures doped with Ni, Pd, Pt, NiPt or NiPd to be novel catalysts for the conversion of solar energy for photocatalytic hydrogen production, since they improve the absorption of solar energy in the range of interest for solar radiation; and act as reaction centers, reducing the required overpotential for hydrogen production from water.

  3. Aerobic Asymmetric Dehydrogenative Cross-Coupling between Two C(sp3)-H Groups Catalyzed by a Chiral-at-Metal Rhodium Complex.

    Science.gov (United States)

    Tan, Yuqi; Yuan, Wei; Gong, Lei; Meggers, Eric

    2015-10-26

    A sustainable C-C bond formation is merged with the catalytic asymmetric generation of one or two stereocenters. The introduced catalytic asymmetric cross-coupling of two C(sp3)-H groups with molecular oxygen as the oxidant profits from the oxidative robustness of a chiral-at-metal rhodium(III) catalyst and exploits an autoxidation mechanism or visible-light photosensitized oxidation. In the latter case, the catalyst serves a dual function, namely as a chiral Lewis acid for catalyzing enantioselective enolate chemistry and at the same time as a visible-light-driven photoredox catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Handheld hydrogen - a new concept for hydrogen storage

    DEFF Research Database (Denmark)

    Johannessen, Tue; Sørensen, Rasmus Zink

    2005-01-01

    A method of hydrogen storage using metal ammine complexes in combination with an ammonia decomposition catalyst is presented. This dense hydrogen storage material has high degree of safety compared to all the other available alternatives. This technology reduces the safety hazards of using liquid...

  5. The role of atomic hydrogen in regulating the scatter of the mass-metallicity relation

    Science.gov (United States)

    Brown, Toby; Cortese, Luca; Catinella, Barbara; Kilborn, Virginia

    2018-01-01

    In this paper, we stack neutral atomic hydrogen (H I) spectra for 9720 star-forming galaxies along the mass-metallicity relation. The sample is selected according to stellar mass (109 ≤ M⋆/M⊙ ≤ 1011) and redshift (0.02 ≤ z ≤ 0.05) from the overlap of the Sloan Digital Sky Survey and Arecibo Legacy Fast ALFA survey. We confirm and quantify the strong anticorrelation between H I mass and gas-phase metallicity at fixed stellar mass. Furthermore, we show for the first time that the relationship between gas content and metallicity is consistent between different metallicity estimators, contrary to the weaker trends found with star formation which are known to depend on the observational techniques used to derive oxygen abundances and star formation rates. When interpreted in the context of theoretical work, this result supports a scenario where galaxies exist in an evolving equilibrium between gas, metallicity and star formation. The fact that deviations from this equilibrium are most strongly correlated with gas mass suggests that the scatter in the mass-metallicity relation is primarily driven by fluctuations in gas accretion.

  6. Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds.

    Science.gov (United States)

    Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

    2015-05-11

    A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Stable catalyst layers for hydrogen permeable composite membranes

    Science.gov (United States)

    Way, J. Douglas; Wolden, Colin A

    2014-01-07

    The present invention provides a hydrogen separation membrane based on nanoporous, composite metal carbide or metal sulfide coated membranes capable of high flux and permselectivity for hydrogen without platinum group metals. The present invention is capable of being operated over a broad temperature range, including at elevated temperatures, while maintaining hydrogen selectivity.

  8. Influences of species of metals and supports on the hydrogenation activity of carbon-supported metal sulfides catalysts; Tanso biryushi tanji shokubai no suisoka kassei ni taisuru kassei kinzoku oyobi tantaishu no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Sakanishi, K.; Hasuo, H.; Taniguchi, H.; Nagamatsu, T.; Mochida, I. [Kyushu University, Fukuoka (Japan). Institute of Advanced Material Study

    1996-10-28

    In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supported catalysts were prepared. Catalytic activities of them were investigated for the hydrogenation of 1-methylnaphthalene, to discuss the influences of metals and carbon species on the catalytic activity. Various water soluble and oil soluble Mo and Ni salts were used for NiMo supported catalysts. Among various carbon supports, Ketjen Black (KB) was effective for preparing the catalyst showing the most excellent hydrogenation activity. The KB and Black Pearl 2000 (BP2000) showing high hydrogenation activity were fine particles having high specific surface area more than 1000 m{sup 2}/g and primary particle diameter around 30 nm. This was inferred to contribute to the high dispersion support of active metals. Since such fine particles of carbon exhibited hydrophobic surface, they were suitable for preparing catalysts from the methanol-soluble metals. Although Ni and Mo added iron-based catalysts provided lower aromatic hydrogenation activity, they exhibited liquefaction activity competing with the NiMo/KB catalyst. 3 refs., 1 fig., 3 tabs.

  9. Study of a dense metal membrane reactor for hydrogen separation from hydroiodic acid decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Tosti, Silvano; Borelli, Rodolfo; Borgognoni, Fabio [ENEA, Dipartimento FPN, C.R. ENEA Frascati, Via E. Fermi 45, Frascati, Roma I-00044 (Italy); Favuzza, Paolo; Tarquini, Pietro [ENEA, Dipartimento TER, C.R. ENEA Casaccia, Via Anguillarese 301, Roma (Italy); Rizzello, Claudio [Tesi Sas, Via Bolzano 28, Roma (Italy)

    2008-10-15

    A membrane reactor has been studied for separating the hydrogen produced by the dissociation of hydroiodic acid in the thermochemical-sulfur iodine process. A dense metal membrane tube of wall thickness 0.250 mm has been considered in this analysis for hosting a fixed-bed catalyst: the selective separation of hydrogen from an azeotropic H{sub 2}O-HI mixture has been studied in the temperature range of 700-800 K. The materials being considered for the construction of the membrane tube are niobium and tantalum; as a matter of fact, the most commonly used Pd-Ag membranes cannot withstand the corrosive environment generated by the hydroiodic acid. The Damkohler-Peclet analysis has been used for designing the membrane reactor, while a finite element method has simulated its behaviour: the effect of the temperature and pressure on the HI conversion and hydrogen yield has been evaluated. (author)

  10. A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Cammarota, Ryan C. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Vollmer, Matthew V. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Xie, Jing [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Ye, Jingyun [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Linehan, John C. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Burgess, Samantha A. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Appel, Aaron M. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Gagliardi, Laura [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Lu, Connie C. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States

    2017-09-28

    Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminal Ni-H, for which the hydride donor strength rivals those of precious metal-hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis. The work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award DE-SC0012702. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Research Fellowship programs, respectively. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  11. Quasi-two-dimensional metallic hydrogen inside di-phosphide at high pressure

    International Nuclear Information System (INIS)

    Degtyarenko, N N; Mazur, E A

    2016-01-01

    The method of mathematical modelling was used for the calculation of the structural, electronic, phononic, and other characteristics of various normal phases of phosphorus hydrides with stoichiometry PH k . It was shown that the di-phosphine may form 2D lattice of the metallic hydrogen in it, stabilized by phosphorus atoms under high hydrostatic pressure. The resulting structure with the elements of H-P-H has a locally stable (or metastable) phonon spectrum. The properties of di-phosphine were compared with the properties of similar structures such as the sulphur hydrides. (paper)

  12. Alcohols as hydrogen-donor solvents for treatment of coal

    Science.gov (United States)

    Ross, David S.; Blessing, James E.

    1981-01-01

    A method for the hydroconversion of coal by solvent treatment at elevated temperatures and pressure wherein an alcohol having an .alpha.-hydrogen atom, particularly a secondary alcohol such as isopropanol, is utilized as a hydrogen donor solvent. In a particular embodiment, a base capable of providing a catalytically effective amount of the corresponding alcoholate anion under the solvent treatment conditions is added to catalyze the alcohol-coal reaction.

  13. Copper(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones.

    Science.gov (United States)

    Xu, Shuai; Gao, Yunpeng; Chen, Ri; Wang, Kang; Zhang, Yan; Wang, Jianbo

    2016-03-25

    The Cu(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones via metal carbene intermediates is reported. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of carbon-carbon double bonds. Mechanistically, Cu(I) carbene formation and subsequent carbene migratory insertion are proposed as the key steps.

  14. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  15. Designer HF-Based Fluorination Reagent: Highly Regioselective Synthesis of Fluoroalkenes and gem-Difluoromethylene Compounds from Alkynes

    Science.gov (United States)

    2015-01-01

    Hydrogen fluoride (HF) and selected nonbasic and weakly coordinating (toward cationic metal) hydrogen-bond acceptors (e.g., DMPU) can form stable complexes through hydrogen bonding. The DMPU/HF complex is a new nucleophilic fluorination reagent that has high acidity and is compatible with cationic metal catalysts. The gold-catalyzed mono- and dihydrofluorination of alkynes using the DMPU/HF complex yields synthetically important fluoroalkenes and gem-difluoromethlylene compounds regioselectively. PMID:25260170

  16. Hydrogen-deuterium exchange reaction of 2-methylpyridine catalyzed by several fatty acids

    International Nuclear Information System (INIS)

    Hirata, Hirohumi; Fukuzumi, Kazuo.

    1976-01-01

    Hydrogen-deuterium exchange reaction of 2-methylpyridine has been studied by using several fatty acids as catalysts. The reaction was carried out in a sealed pyrex tube at 120 0 C, and the contents of the products were determined by mass spectrometry. Reaction of 2-methylpyridine with monodeuteroacetic acid (1 : 1, mol/mol) arrived at a equilibrium (d 0 reversible d 1 reversible d 2 reversible d 3 ) in 2 hr (d 0 41%, d 1 42%, d 2 15%, d 3 2%). No exchange was observed for the reaction of pyridine with monodeuteroacetic acid. The conversion-time curves of typical series reactions (d 0 → d 1 → d 2 → d 3 ) were obtained for the fatty acid catalyzed exchange in deuterium oxide. The effect of the fatty acid RCO 2 H (substrate : fatty acid : D 2 O=1 : 0.86 : 27.6, mol/mol/mol) on the conversion was in the order of R; C 1 --C 3 4 --C 10 , where the reaction mixtures were homogeneous in the case of C 1 --C 3 and were heterogeneous in the case of C 4 --C 10 . The effects of the initial concentration of the substrates and the catalysts (RCO 2 H) on the total conversion were studied by using some fatty acids (R; C 2 , C 4 and C 9 ) in deuterium oxide (for 2 hr). The total conversion of the substrate increases with increasing the concentration of the acids. The total conversion decreases in the case of R=C 9 , but, increases in the case of R=C 2 with increasing the concentration of the substrate. In the case of reactions with low concentrations of the substrate, the reactivity was in the order of C 9 >C 4 >C 2 , while with high concentrations, the reactivity was in the order of C 4 >C 2 >C 9 and C 9 >C 4 >C 2 with high and low concentrations of the acids, respectively. A possible reaction mechanism was proposed and discussed. (auth.)

  17. Asymmetric Hydrogenation of Quinoxalines Catalyzed by Iridium/PipPhos

    NARCIS (Netherlands)

    Mrsic, Natasa; Jerphagnon, Thomas; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.

    2009-01-01

    A catalyst made in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl](2), and the monodentate phosphoramidite ligand (S)-PipPhos was used in the enantioselective hydrogenation of 2- and 2,6-substituted quinoxalines. In the presence of piperidine hydrochloride as additive full

  18. Thick film hydrogen sensor

    Science.gov (United States)

    Hoffheins, Barbara S.; Lauf, Robert J.

    1995-01-01

    A thick film hydrogen sensor element includes an essentially inert, electrically-insulating substrate having deposited thereon a thick film metallization forming at least two resistors. The metallization is a sintered composition of Pd and a sinterable binder such as glass frit. An essentially inert, electrically insulating, hydrogen impermeable passivation layer covers at least one of the resistors.

  19. Metal (Ag/Ti-Containing Hydrogenated Amorphous Carbon Nanocomposite Films with Enhanced Nanoscratch Resistance: Hybrid PECVD/PVD System and Microstructural Characteristics

    Directory of Open Access Journals (Sweden)

    Marios Constantinou

    2018-03-01

    Full Text Available This study aimed to develop hydrogenated amorphous carbon thin films with embedded metallic nanoparticles (a–C:H:Me of controlled size and concentration. Towards this end, a novel hybrid deposition system is presented that uses a combination of Plasma Enhanced Chemical Vapor Deposition (PECVD and Physical Vapor Deposition (PVD technologies. The a–C:H matrix was deposited through the acceleration of carbon ions generated through a radio-frequency (RF plasma source by cracking methane, whereas metallic nanoparticles were generated and deposited using terminated gas condensation (TGC technology. The resulting material was a hydrogenated amorphous carbon film with controlled physical properties and evenly dispersed metallic nanoparticles (here Ag or Ti. The physical, chemical, morphological and mechanical characteristics of the films were investigated through X-ray reflectivity (XRR, Raman spectroscopy, Scanning Electron Microscopy (SEM, Atomic Force Microscopy (AFM, Transmission Electron Microscopy (TEM and nanoscratch testing. The resulting amorphous carbon metal nanocomposite films (a–C:H:Ag and a–C:H:Ti exhibited enhanced nanoscratch resistance (up to +50% and low values of friction coefficient (<0.05, properties desirable for protective coatings and/or solid lubricant applications. The ability to form nanocomposite structures with tunable coating performance by potentially controlling the carbon bonding, hydrogen content, and the type/size/percent of metallic nanoparticles opens new avenues for a broad range of applications in which mechanical, physical, biological and/or combinatorial properties are required.

  20. ACCEPTABILITY ENVELOPE FOR METAL HYDRIDE-BASED HYDROGEN STORAGE SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, B.; Corgnale, C.; Tamburello, D.; Garrison, S.; Anton, D.

    2011-07-18

    The design and evaluation of media based hydrogen storage systems requires the use of detailed numerical models and experimental studies, with significant amount of time and monetary investment. Thus a scoping tool, referred to as the Acceptability Envelope, was developed to screen preliminary candidate media and storage vessel designs, identifying the range of chemical, physical and geometrical parameters for the coupled media and storage vessel system that allow it to meet performance targets. The model which underpins the analysis allows simplifying the storage system, thus resulting in one input-one output scheme, by grouping of selected quantities. Two cases have been analyzed and results are presented here. In the first application the DOE technical targets (Year 2010, Year 2015 and Ultimate) are used to determine the range of parameters required for the metal hydride media and storage vessel. In the second case the most promising metal hydrides available are compared, highlighting the potential of storage systems, utilizing them, to achieve 40% of the 2010 DOE technical target. Results show that systems based on Li-Mg media have the best potential to attain these performance targets.