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Sample records for hydride transfer catalyzed

  1. Hydride transfer made easy in the oxidation of alcohols catalyzed by choline oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Gadda, G.; Orville, A.; Pennati, A.; Francis, K.; Quaye, O.; Yuan, H.; Rungsrisuriyachai, K.; Finnegan, S.; Mijatovic, S.; Nguyen, T.

    2008-06-08

    Choline oxidase (E.C. 1.1.3.17) catalyzes the two-step, four-electron oxidation of choline to glycine betaine with betaine aldehyde as enzyme-associated intermediate and molecular oxygen as final electron acceptor (Scheme 1). The gem-diol, hydrated species of the aldehyde intermediate of the reaction acts as substrate for aldehyde oxidation, suggesting that the enzyme may use similar strategies for the oxidation of the alcohol substrate and aldehyde intermediate. The determination of the chemical mechanism for alcohol oxidation has emerged from biochemical, mechanistic, mutagenetic, and structural studies. As illustrated in the mechanism of Scheme 2, the alcohol substrate is initially activated in the active site of the enzyme by removal of the hydroxyl proton. The resulting alkoxide intermediate is then stabilized in the enzyme-substrate complex via electrostatic interactions with active site amino acid residues. Alcohol oxidation then occurs quantum mechanically via the transfer of the hydride ion from the activated substrate to the N(5) flavin locus. An essential requisite for this mechanism of alcohol oxidation is the high degree of preorganization of the activated enzyme-substrate complex, which is achieved through an internal equilibrium of the Michaelis complex occurring prior to, and independently from, the subsequent hydride transfer reaction. The experimental evidence that support the mechanism for alcohol oxidation shown in Scheme 2 is briefly summarized in the Results and Discussion section.

  2. Benchmarking Quantum Mechanics/Molecular Mechanics (QM/MM) Methods on the Thymidylate Synthase-Catalyzed Hydride Transfer.

    Science.gov (United States)

    Świderek, Katarzyna; Arafet, Kemel; Kohen, Amnon; Moliner, Vicent

    2017-03-14

    Given the ubiquity of hydride-transfer reactions in enzyme-catalyzed processes, identifying the appropriate computational method for evaluating such biological reactions is crucial to perform theoretical studies of these processes. In this paper, the hydride-transfer step catalyzed by thymidylate synthase (TSase) is studied by examining hybrid quantum mechanics/molecular mechanics (QM/MM) potentials via multiple semiempirical methods and the M06-2X hybrid density functional. Calculations of protium and tritium transfer in these reactions across a range of temperatures allowed calculation of the temperature dependence of kinetic isotope effects (KIE). Dynamics and quantum-tunneling effects are revealed to have little effect on the reaction rate, but are significant in determining the KIEs and their temperature dependence. A good agreement with experiments is found, especially when computed for RM1/MM simulations. The small temperature dependence of quantum tunneling corrections and the quasiclassical contribution term cancel each other, while the recrossing transmission coefficient seems to be temperature-independent over the interval of 5-40 °C.

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

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

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

    2016-05-17

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

  5. Cytochrome P450BM-3 reduces aldehydes to alcohols through a direct hydride transfer

    Energy Technology Data Exchange (ETDEWEB)

    Kaspera, Ruediger; Sahele, Tariku; Lakatos, Kyle [Department of Medicinal Chemistry, University of Washington, Box 357610, Seattle, WA 98195-7610 (United States); Totah, Rheem A., E-mail: rtotah@u.washington.edu [Department of Medicinal Chemistry, University of Washington, Box 357610, Seattle, WA 98195-7610 (United States)

    2012-02-17

    Highlights: Black-Right-Pointing-Pointer Cytochrome P450BM-3 reduced aldehydes to alcohols efficiently (k{sub cat} {approx} 25 min{sup -1}). Black-Right-Pointing-Pointer Reduction is a direct hydride transfer from R-NADP{sup 2}H to the carbonyl moiety. Black-Right-Pointing-Pointer P450 domain variants enhance reduction through potential allosteric/redox interactions. Black-Right-Pointing-Pointer Novel reaction will have implications for metabolism of xenobiotics. -- Abstract: Cytochrome P450BM-3 catalyzed the reduction of lipophilic aldehydes to alcohols efficiently. A k{sub cat} of {approx}25 min{sup -1} was obtained for the reduction of methoxy benzaldehyde with wild type P450BM-3 protein which was higher than in the isolated reductase domain (BMR) alone and increased in specific P450-domain variants. The reduction was caused by a direct hydride transfer from preferentially R-NADP{sup 2}H to the carbonyl moiety of the substrate. Weak substrate-P450-binding of the aldehyde, turnover with the reductase domain alone, a deuterium incorporation in the product from NADP{sup 2}H but not D{sub 2}O, and no inhibition by imidazole suggests the reductase domain of P450BM-3 as the potential catalytic site. However, increased aldehyde reduction by P450 domain variants (P450BM-3 F87A T268A) may involve allosteric or redox mechanistic interactions between heme and reductase domains. This is a novel reduction of aldehydes by P450BM-3 involving a direct hydride transfer and could have implications for the metabolism of endogenous substrates or xenobiotics.

  6. Another Look at the Mechanisms of Hydride Transfer Enzymes with Quantum and Classical Transition Path Sampling.

    Science.gov (United States)

    Dzierlenga, Michael W; Antoniou, Dimitri; Schwartz, Steven D

    2015-04-02

    The mechanisms involved in enzymatic hydride transfer have been studied for years, but questions remain due, in part, to the difficulty of probing the effects of protein motion and hydrogen tunneling. In this study, we use transition path sampling (TPS) with normal mode centroid molecular dynamics (CMD) to calculate the barrier to hydride transfer in yeast alcohol dehydrogenase (YADH) and human heart lactate dehydrogenase (LDH). Calculation of the work applied to the hydride allowed for observation of the change in barrier height upon inclusion of quantum dynamics. Similar calculations were performed using deuterium as the transferring particle in order to approximate kinetic isotope effects (KIEs). The change in barrier height in YADH is indicative of a zero-point energy (ZPE) contribution and is evidence that catalysis occurs via a protein compression that mediates a near-barrierless hydride transfer. Calculation of the KIE using the difference in barrier height between the hydride and deuteride agreed well with experimental results.

  7. Heat transfer analysis of metal hydrides in metal-hydrogen secondary batteries

    Science.gov (United States)

    Onischak, M.; Dharia, D.; Gidaspow, D.

    1976-01-01

    The heat transfer between a metal-hydrogen secondary battery and a hydrogen-storing metal hydride was studied. Temperature profiles of the endothermic metal hydrides and the metal-hydrogen battery were obtained during discharging of the batteries assuming an adiabatic system. Two hydride materials were considered in two physical arrangements within the battery system. In one case the hydride is positioned in a thin annular region about the battery stack; in the other the hydride is held in a tube down the center of the stack. The results show that for a typical 20 ampere-hour battery system with lanthanum pentanickel hydride as the hydrogen reservoir the system could perform successfully.

  8. Iron Hydride Detection and Intramolecular Hydride Transfer in a Synthetic Model of Mono-Iron Hydrogenase with a CNS Chelate.

    Science.gov (United States)

    Durgaprasad, Gummadi; Xie, Zhu-Lin; Rose, Michael J

    2016-01-19

    We report the identification and reactivity of an iron hydride species in a synthetic model complex of monoiron hydrogenase. The hydride complex is derived from a phosphine-free CNS chelate that includes a Fe-C(NH)(═O) bond (carbamoyl) as a mimic of the active site iron acyl. The reaction of [((O═)C(HN)N(py)S(Me))Fe(CO)2(Br)] (1) with NaHBEt3 generates the iron hydride intermediate [((O═)C(HN)N(py)S(Me))Fe(H)(CO)2] (2; δFe-H = -5.08 ppm). Above -40 °C, the hydride species extrudes CH3S(-) via intramolecular hydride transfer, which is stoichiometrically trapped in the structurally characterized dimer μ2-(CH3S)2-[((O═)C(HN)N(Ph))Fe(CO)2]2 (3). Alternately, when activated by base ((t)BuOK), 1 undergoes desulfurization to form a cyclometalated species, [((O═)C(NH)NC(Ph))Fe(CO)2] (5); derivatization of 5 with PPh3 affords the structurally characterized species [((O═)C(NH)NC)Fe(CO)(PPh3)2] (6), indicating complex 6 as the common intermediate along each pathway of desulfurization.

  9. Concerted proton-coupled electron transfer from a metal-hydride complex.

    Science.gov (United States)

    Bourrez, Marc; Steinmetz, Romain; Ott, Sascha; Gloaguen, Frederic; Hammarström, Leif

    2014-02-01

    Metal hydrides are key intermediates in the catalytic reduction of protons and CO2 as well as in the oxidation of H2. In these reactions, electrons and protons are transferred to or from separate acceptors or donors in bidirectional protoncoupled electron transfer (PCET) steps. The mechanistic interpretation of PCET reactions of metal hydrides has focused on the stepwise transfer of electrons and protons. A concerted transfer may, however, occur with a lower reaction barrier and therefore proceed at higher catalytic rates. Here we investigate the feasibility of such a reaction by studying the oxidation–deprotonation reactions of a tungsten hydride complex. The rate dependence on the driving force for both electron transfer and proton transfer—employing different combinations of oxidants and bases—was used to establish experimentally the concerted, bidirectional PCET of a metal-hydride species. Consideration of the findings presented here in future catalyst designs may lead to more-efficient catalysts.

  10. Experimental comparison on heat transfer-enhancing component of metal hydride bed

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Hyun-goo, E-mail: hgkang@nfri.re.kr; Chung, Dong-you; Oh, Yun Hee; Chang, Min Ho; Yun, Sei-Hun

    2016-11-01

    Highlights: • Two small ZrCo metal hydride beds were developed. • Copper foam or fin as heat transfer-enhancing component are experimentally compared. • Copper foam bed is more efficient for uniform and rapid heating of metal hydride. • Copper foam bed is more efficient in removal of reaction heat during absorption. - Abstract: Metal hydride bed will be one of the key components for safe handling of tritium in fusion fuel cycle. In case of normal or emergency shutdown of fuel cycle, metal hydride bed installed in storage and delivery system (SDS) of tritium plant will absorb tritium gas in the system as soon as possible. Supply of hydrogen isotope gas to fueling system of fusion reactor will start from the metal hydride beds. Rapid delivery, rapid recovery including rapid heating and cooling are key issues. For better performance of metal hydride bed, various forms of heat transfer enhancing component or design can be applied. This study aims to help the selection of heat transfer enhancing component. Two small ZrCo beds with copper foam and copper fin were developed and experimented with hydrogen gas. Recovery and delivery performance, heating and cooling performance are compared. Experimental results show metal hydride bed with copper foam has improved performance. Uniform heating of metal hydride during desorption and removal of reaction heat during absorption are more efficient with copper foam bed than copper fin bed.

  11. Iridium-Catalyzed Hydrogen Transfer Reactions

    Science.gov (United States)

    Saidi, Ourida; Williams, Jonathan M. J.

    This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

  12. Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel.

    Science.gov (United States)

    Connelly Robinson, Samantha J; Zall, Christopher M; Miller, Deanna L; Linehan, John C; Appel, Aaron M

    2016-06-14

    The thermodynamic hydricity of a metal hydride can vary considerably between solvents. This parameter can be used to determine the favourability of a hydride-transfer reaction, such as the reaction between a metal hydride and CO2 to produce formate. Because the hydricities of these species do not vary consistently between solvents, reactions that are thermodynamically unfavourable in one solvent can be favourable in others. The hydricity of a water-soluble, bis-phosphine nickel hydride complex was compared to the hydricity of formate in water and in acetonitrile. Formate is a better hydride donor than [HNi(dmpe)2](+) by 7 kcal mol(-1) in acetonitrile, and no hydride transfer from [HNi(dmpe)2](+) to CO2 occurs in this solvent. The hydricity of [HNi(dmpe)2](+) is greatly improved in water relative to acetonitrile, in that reduction of CO2 to formate by [HNi(dmpe)2](+) was found to be thermodynamically downhill by 8 kcal mol(-1). Catalysis for the hydrogenation of CO2 was pursued, but the regeneration of [HNi(dmpe)2] under catalytic conditions was unfavourable. However, the present results demonstrate that the solvent dependence of thermodynamic parameters such as hydricity and acidity can be exploited in order to produce systems with balanced or favourable overall thermodynamics. This approach should be advantageous for the design of future water-soluble catalysts.

  13. Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger

    Science.gov (United States)

    Oi, Tsutomu; Maki, Kohei; Sakaki, Yoshinori

    Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger were investigated. Metal hydride beds were filled with AB 2 type hydrogen-storage alloy's particles, Ti 0.42Zr 0.58Cr 0.78Fe 0.57Ni 0.2Mn 0.39Cu 0.03, with a storage capacity of 0.92 wt.%. Heat transfer model in the metal hydride bed based on the heat transfer mechanism for packed bed proposed by Kunii and co-workers is presented. The time-dependent hydrogen absorption/desorption rate and pressure in the metal hydride vessel calculated by the model were compared with the experimental results. During the hydriding, calculated hydrogen absorption rates agreed with measured ones. Calculated thermal equilibrium hydrogen pressures were slightly lower than the measured hydrogen pressures at the inlet of metal hydride vessel. Taking account of the pressure gradient between the inlet of metal hydride vessel and the metal hydride bed, it is considered that this discrepancy is reasonable. During the dehydriding, there were big differences between the calculated hydrogen desorption rates and measured ones. As calculated hydrogen desorption rates were lower than measured ones, there were big differences between the calculated thermal equilibrium hydrogen pressures and the measured hydrogen pressures at the inlet of metal hydride vessel. It is considered that those differences are due to the differences of the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity between the assumed and actual ones. It is important to obtain the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity both during the hydriding and dehydriding to design a metal hydride vessel.

  14. Direct generation of oxygen-stabilized radicals by H• transfer from transition metal hydrides.

    Science.gov (United States)

    Kuo, Jonathan L; Hartung, John; Han, Arthur; Norton, Jack R

    2015-01-28

    Transition-metal hydrides generate α-alkoxy radicals by H• transfer to enol ethers. We have measured the rate constant for transfer from CpCr(CO)3H to n-butyl vinyl ether and have examined the chemistry of radicals generated by such transfers. Radicals from appropriate substrates undergo 5-exo cyclization, with higher diastereoselectivity than the analogous all-carbon radicals. From such radicals it is straightforward to make substituted tetrahydrofurans.

  15. Theoretical kinetic isotope effects for the hydride-transfer step in lactate dehydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Andres, J.; Moliner, V.; Safont, V.S. (Universitat Jaume I, Castellon (Spain). Dept. die Ciencies Experimentals)

    1994-06-21

    The transition-state (TS) structure for the hydride transfer in lactate dehydrogenase (LHD) enzyme has been calculated with analytical gradients at MNDO, AM1 and PM3 semiempirical levels. The TS is a first-order saddle point on the hypersurface. (Author).

  16. Synthesis of Oxacyclic Scaffolds via Dual Ruthenium Hydride/Brønsted Acid‐Catalyzed Isomerization/Cyclization of Allylic Ethers

    DEFF Research Database (Denmark)

    Ascic, Erhad; Ohm, Ragnhild Gaard; Petersen, Rico;

    2014-01-01

    A ruthenium hydride/Brønsted acid‐catalyzed tandem sequence is reported for the synthesis of 1,3,4,9‐tetrahydropyrano[3,4‐b]indoles (THPIs) and related oxacyclic scaffolds. The process was designed on the premise that readily available allylic ethers would undergo sequential isomerization, first ...

  17. Computational study of alkynes insertion into metal-hydride bonds catalyzed by bimetallic complexes.

    Science.gov (United States)

    Di Tommaso, Stefania; Tognetti, Vincent; Sicilia, Emilia; Adamo, Carlo; Russo, Nino

    2010-11-01

    Density Functional Theory investigations on the insertion mechanism of phenylacetylene into metal-hydride bonds in bimetallic (Pt,Os) catalysts have been carried out. The results obtained have been also compared with the non-reactive monometallic (Os-based) system, to elucidate the cooperative effects and to explain the observed absence of reactivity. The identified reaction path involves phenylacetylene coordination followed by the insertion into the metal-hydride bond, leading to the formation of the experimentally observed products. Both steps do not require large energies compatible with the experimental conditions. The comparison with the reaction path for the monometallic species gives some hints on the cooperative effects due to the presence of the second metal which is related to its role in the CO release for creating a coordination site for phenylacetylene and not in the insertion energetics. The calculations provide a detailed analysis of the reaction complexity and provide a rationale for the efficiency of the process.

  18. Transition-metal-free coupling reaction of vinylcyclopropanes with aldehydes catalyzed by tin hydride.

    Science.gov (United States)

    Ieki, Ryosuke; Kani, Yuria; Tsunoi, Shinji; Shibata, Ikuya

    2015-04-13

    Donor-acceptor cyclopropanes are useful building blocks for catalytic cycloaddition reactions with a range of electrophiles to give various cyclic products. In contrast, relatively few methods are available for the synthesis of homoallylic alcohols through coupling of vinylcyclopropanes (VCPs) with aldehydes, even with transition-metal catalysts. Here, we report that the hydrostannation of vinylcyclopropanes (VCPs) was effectively promoted by dibutyliodotin hydride (Bu2 SnIH). The resultant allylic tin compounds reacted easily with aldehydes. Furthermore, the use of Bu2 SnIH was effectively catalytic in the presence of hydrosilane as a hydride source, which established a coupling reaction of VCPs with aldehydes for the synthesis of homoallylic alcohols without the use of transition-metal catalysts. In contrast to conventional catalytic reactions of VCPs, the presented method allowed the use of several VCPs in addition to conventional donor-acceptor cyclopropanes.

  19. Anode properties of magnesium hydride catalyzed with niobium oxide for an all solid-state lithium-ion battery.

    Science.gov (United States)

    Ikeda, Suguru; Ichikawa, Takayuki; Kawahito, Koji; Hirabayashi, Kazuhiro; Miyaoka, Hiroki; Kojima, Yoshitsugu

    2013-08-18

    The anode properties of pristine MgH2 and MgH2 catalyzed with Nb2O5 have been investigated for an all solid-state lithium-ion battery. The catalytic effect stabilizes the plateau voltage as a result of kinetic improvement of the hydrogen transfer from the Mg phase to the Li phase.

  20. Transfer Methane to Fragrant Hydrocarbon by Direct Catalyzed Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ Sponsored by NSFC,a research project -"Transfer methane to fragrant hydrocarbon by direct catalyzed dehydrogenation",directed by Prof.Xin Bao from Dalian Institute of Chemical Physics of CAS,honored the 2nd class National Science & Technology Award in 2005.

  1. Rules and trends of metal cation driven hydride-transfer mechanisms in metal amidoboranes.

    Science.gov (United States)

    Kim, Dong Young; Lee, Han Myoung; Seo, Jongcheol; Shin, Seung Koo; Kim, Kwang S

    2010-01-01

    Group I and II metal amidoboranes have been identified as one of the promising families of materials for efficient H(2) storage. However, the underlying mechanism of the dehydrogenation of these materials is not well understood. Thus, the mechanisms and kinetics of H(2) release in metal amidoboranes are investigated using high level ab initio calculations and kinetic simulations. The metal plays the role of catalyst for the hydride transfer with formation of a metal hydride intermediate towards the dehydrogenation. In this process, with increasing ionic character of the metal hydride bond in the intermediate, the stability of the intermediate decreases, while the dehydrogenation process involving ionic recombination of the hydridic H with the protic H proceeds with a reduced barrier. Such correlations lead directly to a U-shaped relationship between the activation energy barrier for H(2) elimination and the ionicity of metal hydride bond. Oligomerized intermediates are formed by the chain reaction of the size-driven catalytic effects of metals, competing with the non-oligomerization pathway. The kinetic rates at low temperatures are determined by the maximum barrier height in the pathway (a Lambda-shaped relation), while those at moderately high temperatures are determined by most of multiple-barriers. This requires kinetic simulations. At the operating temperatures of proton exchange membrane fuel cells, the metal amidoboranes with lithium and sodium release H(2) along both oligomerization and non-oligomerization paths. The sodium amidoboranes show the most accelerated rates, while others release H(2) at similar rates. In addition, we predict that the novel metal amidoborane-based adducts and mixtures would release H(2) with accelerated rates as well as with enhanced reversibility. This comprehensive study is useful for further developments of active metal-based better hydrogen storage materials.

  2. A variety of electrostatic interactions and adducts can activate NAD(P) cofactors for hydride transfer.

    Science.gov (United States)

    Meijers, Rob; Cedergren-Zeppezauer, Eila

    2009-03-16

    In NAD(P)-dependent enzymes the coenzyme gives or takes a hydride ion, but how the nicotinamide ring is activated to form the transition state for hydride transfer is not clear. On the basis of ultra-high resolution X-ray crystal structures of liver alcohol dehydrogenase (LADH) in complex with NADH and a number of substrate analogues we proposed that the activation of NADH is an integral part of the enzyme mechanism of aldehyde reduction [R. Meijers, R.J. Morris, H.W. Adolph, A. Merli, V.S. Lamzin, E.S. Cedergren-Zeppezauer, On the enzymatic activation of NADH, The Journal of Biological Chemistry 276(12) (2001) 9316-9321, %U http://www.ncbi.nlm.nih.gov/pubmed/11134046; R. Meijers, H.-W. Adolph, Z. Dauter, K.S. Wilson, V.S. Lamzin, E.S. Cedergren-Zeppezauer, Structural evidence for a ligand coordination switch in liver alcohol dehydrogenase, Biochemistry 46(18) (2007) 5446-5454, %U http://www.ncbi.nlm.nih.gov/pubmed/17429946]. We observed a nicotinamide with a severely distorted pyridine ring and a water molecule in close proximity to the ring. Quantum chemical calculations indicated that (de)protonation of the water molecule can be directly coupled to activation of NADH for hydride transfer. A systematic search of the Protein Data Bank (PDB) for atoms that come within van der Waals distance of the pyridine ring of the nicotinamide reveals that a large number of NAD(P)-containing protein complexes are involved in electrostatic interactions with the enzymatic environment. Using the deposited diffraction data to analyze the cofactor and its surroundings, we observe several adducts between protein atoms and the pyridine ring that were not previously reported. This further indicates that the enzymatic activation of NAD(P) induced by electrostatic interactions is an essential part of the hydride transfer mechanism.

  3. Highly diastereo- and regioselective transition metal-catalyzed additions of metal hydrides and bimetallic species to cyclopropenes: easy access to multisubstituted cyclopropanes.

    Science.gov (United States)

    Trofimov, Alexander; Rubina, Marina; Rubin, Michael; Gevorgyan, Vladimir

    2007-11-09

    The first highly efficient, diastereo- and regioselective transition metal-catalyzed addition of metal hydrides (stannanes, silanes, and germanes) and bimetallic species (ditins and silyltins) to cyclopropenes has been developed. It was shown that the addition across the double bond of cyclopropenes is generally controlled by steric factors and proceeds from the least hindered face. This methodology represents a powerful and atom-economic approach toward a wide variety of highly substituted stereodefined cyclopropylmetals, useful building blocks unavailable by other methods.

  4. Coenzyme binding and hydride transfer in Rhodobacter capsulatus ferredoxin/flavodoxin NADP(H) oxidoreductase.

    Science.gov (United States)

    Bortolotti, Ana; Pérez-Dorado, Inmaculada; Goñi, Guillermina; Medina, Milagros; Hermoso, Juan A; Carrillo, Néstor; Cortez, Néstor

    2009-02-01

    Ferredoxin-NADP(H) reductases catalyse the reversible hydride/electron exchange between NADP(H) and ferredoxin/flavodoxin, comprising a structurally defined family of flavoenzymes with two distinct subclasses. Those present in Gram-negative bacteria (FPRs) display turnover numbers of 1-5 s(-1) while the homologues of cyanobacteria and plants (FNRs) developed a 100-fold activity increase. We investigated nucleotide interactions and hydride transfer in Rhodobacter capsulatus FPR comparing them to those reported for FNRs. NADP(H) binding proceeds as in FNRs with stacking of the nicotinamide on the flavin, which resulted in formation of charge-transfer complexes prior to hydride exchange. The affinity of FPR for both NADP(H) and 2'-P-AMP was 100-fold lower than that of FNRs. The crystal structure of FPR in complex with 2'-P-AMP and NADP(+) allowed modelling of the adenosine ring system bound to the protein, whereas the nicotinamide portion was either not visible or protruding toward solvent in different obtained crystals. Stabilising contacts with the active site residues are different in the two reductase classes. We conclude that evolution to higher activities in FNRs was partially favoured by modification of NADP(H) binding in the initial complexes through changes in the active site residues involved in stabilisation of the adenosine portion of the nucleotide and in the mobile C-terminus of FPR.

  5. Nanoparticulate-catalyzed oxygen transfer processes

    Science.gov (United States)

    Hunt, Andrew T.; Breitkopf, Richard C.

    2009-12-01

    Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

  6. Hydrogen desorption properties of magnesium hydride catalyzed multiply with carbon and silicon

    Energy Technology Data Exchange (ETDEWEB)

    Klimkowicz, Alicja [AGH University of Science and Technology Faculty of Energy and Fuels, al. A. Mickiewicza 30, 30-059 Krakow (Poland); Shibaura Institute of Technology, Department of Engineering Science and Mechanics, 3-7-5 Toyosu, Koto-ku 135-8548, Tokyo (Japan); Takasaki, Akito, E-mail: takasaki@sic.shibaura-it.ac.jp [Shibaura Institute of Technology, Department of Engineering Science and Mechanics, 3-7-5 Toyosu, Koto-ku 135-8548, Tokyo (Japan); Gondek, Łukasz; Figiel, Henryk [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. A. Mickiewicza 30, 30-059 Krakow (Poland); Świerczek, Konrad [AGH University of Science and Technology Faculty of Energy and Fuels, al. A. Mickiewicza 30, 30-059 Krakow (Poland)

    2015-10-05

    Highlights: • Crystal structure of 2 mol MgH{sub 2} + (1 − X) mol C + X mol Si (for X = 0, 0.25, 0.5, 0.75 and 1). • Enhanced hydrogen desorption properties. • Lowered temperature of hydrogen desorption for MgH{sub 2} with the multiple addition of C and Si. • Distribution of Si and C on MgH{sub 2} particles after mechanical milling. - Abstract: Magnesium hydride (MgH{sub 2}) is considered as one of hydrogen storage materials. However, the application is limited because of slow hydrogen kinetics and high thermodynamic stability. In this study, MgH{sub 2} powders were mechanically milled with graphite (C) and/or silicon (Si) powders, and effect of multiple addition of C and Si on hydrogen desorption properties was investigated. The multiple addition caused a decrease of the hydrogen desorption (onset and peak) temperatures more than single addition, and the lowest activation energy for hydrogen desorption, 62 kJ/mol, was obtained from sample powders of (2 mol MgH{sub 2} + 0.5 mol C + 0.5 mol Si). The surface of the sample powders after mechanical milling revealed a good distribution of C on the MgH{sub 2} surface and a presence of finer Si particles.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-28

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

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

    Science.gov (United States)

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

    2016-04-13

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

  9. A thermodynamic and kinetic study of hydride transfer of a caffeine derivative.

    Science.gov (United States)

    Han, Xiaozhen; Hao, Weifang; Zhu, Xiao-Qing; Parker, Vernon D

    2012-08-03

    One representative type of heterocyclic compound that can release a hydride ion is 7,8-dihydro-9-methylcaffeine (CAFH). The one-electron oxidation potential of CAFH [-0.294 (V vs Fc(+/0))] and the one-electron reduction potential of CAF(+) [-2.120 (V vs Fc(+/0))] were obtained using two different methods, CV and OSWV. Applying titration calorimetry data in thermodynamic cycles, the enthalpies of CAFH releasing a hydride ion [57.6 kcal/mol] and releasing a hydrogen atom [80.3 kcal/mol] and of its radical cation CAFH(•+) releasing a proton [33.0 kcal/mol] and releasing a hydrogen atom [38.4 kcal/mol] have been determined. Several conclusions can be drawn from the thermodynamic results: (1) CAFH is a very good single-electron donor whose single-electron oxidation potential is much less positive than that of NAD(P)H model compound BNAH [E(ox) = 0.219 V vs Fc(+/0)]. (2) The single-electron reduction potential of CAF(+) is much more negative than that of BNA(+) [E(red) = -1.419 V], which means that CAF(+) is not a good electron acceptor. Furthermore, CAFH is a very good hydride donor compared to BNAH. The results of non-steady-state kinetic studies, for the reaction of CAFH and AcrH(+)ClO(4)(-), show that the ratio of t(0.50)/t(0.05) is larger than 13.5 and the ratio of k(init)/k(pfo) is larger than 1. The pseudo-first-order rate constants obtained at different reaction stages decrease with the time, and the kinetic isotope was observed to be small at a short reaction time and slowly increases to 3.72 with the progress of the reaction. These kinetic results clearly display that the hydride transfer of CAFH to AcrH(+) in acetonitrile is not a one-step mechanism, while the thermodynamic results show that CAFH is a very good electron donor. The combination of the kinetic results with the thermodynamics analysis shows that the hydride transfer of the caffeine derivative CAFH takes place by a two-step reversible mechanism and there is an intermediate in the reaction.

  10. Bio-inspired transition metal-organic hydride conjugates for catalysis of transfer hydrogenation: experiment and theory.

    Science.gov (United States)

    McSkimming, Alex; Chan, Bun; Bhadbhade, Mohan M; Ball, Graham E; Colbran, Stephen B

    2015-02-09

    Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI(+) ) organic hydride-acceptor domain has been coupled with a 1,10-phenanthroline (phen) metal-binding domain to afford a novel multifunctional ligand (L(BI+) ) with hydride-carrier capacity (L(BI+) +H(-) ⇌L(BI) H). Complexes of the type [Cp*M(L(BI) )Cl][PF6 ]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir(III) congener, X-ray crystallography. [Cp*Rh(L(BI) )Cl][PF6 ]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(L(BI) )Cl][PF6 ] and [Cp*M(phen)Cl][PF6 ] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate-driven RhH formation (90 kJ mol(-1) free-energy barrier), transfer of hydride between the Rh and BI(+) centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back-transfer of hydride from the BIH organic hydride donor to the Rh-activated imine substrate (89 kJ mol(-1) barrier), and exergonic protonation of the metal-bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.

  11. Local bonding and atomic environments in Ni-catalyzed complex hydrides.

    Science.gov (United States)

    Graetz, J; Chaudhuri, S; Salguero, T T; Vajo, J J; Meyer, M S; Pinkerton, F E

    2009-05-20

    The local bonding and atomic environments in the Ni-catalyzed destabilized system LiBH4/MgH2 and the quaternary borohydride-amide phase Li3BN2H8, were studied by x-ray absorption spectroscopy. In both cases the Ni catalyst was introduced as NiCl2 and a qualitative comparison of the Ni K-edge near-edge structure suggests the Ni2+ is reduced to primarily Ni0 after ball milling. The extended fine structure of the Ni K edge indicates that the Ni is coordinated by approximately 3 boron atoms with an interatomic distance of approximately 2.1 A and approximately 11 Ni atoms in a split shell at around 2.5 and 2.8 A. These results, and the lack of long-range order, suggest that the Ni is present as a disordered nanocluster with a local structure similar to that of Ni3B. In the fully hydrogenated phase of LiBH4/MgH2 a small amount Mg2NiHx was also present. Surface calculations performed using density functional theory suggest that the lowest kinetic barrier for H2 chemisorption occurs on the Ni3B(100) surface.

  12. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian

    2016-04-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

  13. Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard;

    2013-01-01

    This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

  14. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    Science.gov (United States)

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

  15. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8.

    Science.gov (United States)

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2014-12-28

    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays.

  16. Organocatalytic Synthesis of Tetrahydroquinolines from α,β-Unsaturated Ketones via 1,5-Hydride Transfer/Cyclization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2013-11-15

    We have presented the example of a organo-catalytic enantioselective hydride transfer/cyclization reaction cascade from cyclic amines containing α,β-unsaturated ketones. The synthetically useful ring-fused tetrahydroquinoline derivatives were obtained in moderate to high yields with moderate to high diastereoselectivities. Further investigations for an asymmetric version of this organocatalytic intramolecular redox reaction of α,β-unsaturated ketones are currently underway in our laboratory. The development for direct functionalization of sp{sup 3} C-H bonds has become an area of intense interest in synthetic organic chemistry. Because such reactions offer practical methods for the construction of structurally complex and biologically active organic molecules with atom- and step economy. The 1,5-hydride transfer and subsequent cyclization process is a well-known sp{sup 3} C-H bond function-alization strategy and has attracted considerable interest for its application in the synthesis of heterocyclic compounds.

  17. Titanium-Beta Zeolites Catalyze the Stereospecific Isomerization of D-Glucose to L-Sorbose via Intramolecular C5-C1 Hydride Shift

    Energy Technology Data Exchange (ETDEWEB)

    Gounder, Rajamani [California Inst. of Technology (CalTech), Pasadena, CA (United States); Davis, Mark E. [California Inst. of Technology (CalTech), Pasadena, CA (United States)

    2013-06-03

    Pure-silica zeolite beta containing Lewis acidic framework Ti4+ centers (Ti-Beta) is shown to catalyze the isomerization of D-glucose to L-sorbose via an intramolecular C5–C1 hydride shift. Glucose–sorbose isomerization occurs in parallel to glucose–fructose isomerization on Ti-Beta in both water and methanol solvents, with fructose formed as the predominant product in water and sorbose as the predominant product in methanol (at 373 K) at initial times and over the course of >10 turnovers. Isotopic tracer studies demonstrate that 13C and D labels placed respectively at the C1 and C2 positions of glucose are retained respectively at the C6 and C5 positions of sorbose, consistent with its formation via an intramolecular C5–C1 hydride shift isomerization mechanism. This direct Lewis acid-mediated pathway for glucose–sorbose isomerization appears to be unprecedented among heterogeneous or biological catalysts and sharply contrasts indirect base-mediated glucose–sorbose isomerization via 3,4-enediol intermediates or via retro-aldol fragmentation and recombination of sugar fragments. Measured first-order glucose–sorbose isomerization rate constants (per total Ti; 373 K) for Ti-Beta in methanol are similar for glucose and glucose deuterated at the C2 position (within a factor of ~1.1), but are a factor of ~2.3 lower for glucose deuterated at each carbon position, leading to H/D kinetic isotope effects expected for kinetically relevant intramolecular C5–C1 hydride shift steps. Optical rotation measurements show that isomerization of D-(+)-glucose (92% enantiomeric purity) with Ti-Beta in water (373 K) led to the formation of L-(-)-sorbose (73% enantiomeric purity) and D-(-)-fructose (87% enantiomeric purity) as the predominant stereoisomers, indicating that stereochemistry is preserved at carbon centers not directly involved in intramolecular C5–C1 or C2–C1 hydride shift steps, respectively. This new Lewis acid

  18. Insights into dehydrogenative coupling of alcohols and amines catalyzed by a (PNN)-Ru(II) hydride complex: unusual metal-ligand cooperation.

    Science.gov (United States)

    Zeng, Guixiang; Li, Shuhua

    2011-11-07

    Density functional theory calculations were performed to elucidate the mechanism of dehydrogenative coupling of primary alcohols and amines mediated by a PNN-Ru(II) hydride complex (PNN = (2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine)). A plausible reaction pathway was proposed which contains three stages: (1) The alcohol dehydrogenation reaction to generate the aldehyde and H(2); (2) The aldehyde-amine condensation reaction to form the hemiaminal intermediate; (3) The dehydrogenation process of the hemiaminal intermediate to yield the final amide product with the liberation of H(2). The first and third stages occur via a similar pathway: (a) Proton transfer from the substrate to the PNN ligand; (b) Intramolecular rearrangement of the deprotonated substrate to form an anagostic complex; (c) Hydride transfer from the deprotonated substrate to the Ru center to yield the trans-dihydride intermediate and the aldehyde (or amide); (d) Benzylic proton migration from the PNN ligand to the metal center forming a dihydrogen complex and subsequent H(2) liberation to regenerate the catalyst. In all these steps, the metal-ligand cooperation plays an essential role. In proton transfer steps (a) and (d), the metal-ligand cooperation is achieved through the aromatization/dearomatization processes of the PNN ligand. While in steps (b) and (c), their collaboration are demonstrated by the formation of an anagostic interaction between Ru and the C-H bond and two ionic hydrogen bonds supported by the PNN ligand.

  19. Construction of cyclic enones via gold-catalyzed oxygen transfer reactions

    Directory of Open Access Journals (Sweden)

    Gerald B. Hammond

    2011-05-01

    Full Text Available During the last decade, gold-catalyzed reactions have become a tour de force in organic synthesis. Recently, the gold-, Brønsted acid- or Lewis acid-catalyzed oxygen transfer from carbonyl to carbon–carbon triple bond, the so-called alkyne–carbonyl metathesis, has attracted much attention because this atom economical transformation generates α,β-unsaturated carbonyl derivatives which are of great interest in synthetic organic chemistry. This mini-review focuses on the most recent achievements on gold-catalyzed oxygen transfer reactions of tethered alkynones, diynes or alkynyl epoxides to cyclic enones. The corresponding mechanisms for the transformations are also discussed.

  20. Neutral transition metal hydrides as acids in hydrogen bonding and proton transfer: media polarity and specific solvation effects.

    Science.gov (United States)

    Levina, Vladislava A; Filippov, Oleg A; Gutsul, Evgenii I; Belkova, Natalia V; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S

    2010-08-18

    Structural, spectroscopic, and electronic features of weak hydrogen-bonded complexes of CpM(CO)(3)H (M = Mo (1a), W (1b)) hydrides with organic bases (phosphine oxides R(3)PO (R = n-C(8)H(17), NMe(2)), amines NMe(3), NEt(3), and pyridine) are determined experimentally (variable temperature IR) and computationally (DFT/M05). The intermediacy of these complexes in reversible proton transfer is shown, and the thermodynamic parameters (DeltaH degrees , DeltaS degrees ) of each reaction step are determined in hexane. Assignment of the product ion pair structure is made with the help of the frequency calculations. The solvent effects were studied experimentally using IR spectroscopy in CH(2)Cl(2), THF, and CH(3)CN and computationally using conductor-like polarizable continuum model (CPCM) calculations. This complementary approach reveals the particular importance of specific solvation for the hydrogen-bond formation step. The strength of the hydrogen bond between hydrides 1 and the model bases is similar to that of the M-H...X hydrogen bond between 1 and THF (X = O) or CH(3)CN (X = N) or between CH(2)Cl(2) and the same bases. The latter competitive weak interactions lower the activities of both the hydrides and the bases in the proton transfer reaction. In this way, these secondary effects shift the proton transfer equilibrium and lead to the counterintuitive hampering of proton transfer upon solvent change from hexane to moderately polar CH(2)Cl(2) or THF.

  1. Hydrogen bonding and proton transfer to ruthenium hydride complex CpRuH(dppe): metal and hydride dichotomy.

    Science.gov (United States)

    Silantyev, Gleb A; Filippov, Oleg A; Tolstoy, Peter M; Belkova, Natalia V; Epstein, Lina M; Weisz, Klaus; Shubina, Elena S

    2013-02-18

    The combination of variable temperature (190-297 K) IR and NMR spectroscopy studies with quantum-chemical calculations at the DFT/B3PW91 and AIM level had the aim to determine the mechanism of proton transfer to CpRuH(dppe) (1, dppe = Ph(2)P(CH(2))(2)PPh(2)) and the structures of intermediates. Dihydrogen bond (DHB) formation was established in the case of interaction with weak proton donors like CF(3)CH(2)OH. Low-temperature protonation (at about 200 K) by stronger proton donors leads via DHB complex to the cationic nonclassical complex [CpRu(η(2)-H(2))(dppe)](+) (2). Thermodynamic parameters of DHB formation (for CF(3)CH(2)OH: ΔH°(HB) = -4.9 ± 0.2 kcal·mol(-1), ΔS°(HB) = -17.8 ± 0.7 cal·mol(-1)·K(-1)) and proton transfer (for (CF(3))(2)CHOH: ΔH°(PT) = -5.2 ± 0.3 kcal·mol(-1), ΔS°(PT) = -23 ± 1 cal·mol(-1)·K(-1)) were determined. Above 240 K 2 transforms into trans-[CpRu(H)(2)(dppe)](+) (3) yielding a mixture of 2 and 3 in 1:2 ratio. Kinetic analysis and activation parameters for the "[Ru(η(2)-H(2))](+) → trans-[Ru(H)(2)](+)" transformation indicate reversibility of this process in contrast to irreversible intramolecular isomerization of the Cp* analogue. Calculations show that the driving force of this process is greater stability (by 1.5 kcal·mol(-1) in ΔE scale) of the dihydride cation in comparison with the dihydrogen complex. The calculations of the potential energy profile indicate the low barrier for deprotonation of 2 suggesting that the formation of trans-[CpRu(H)(2)(dppe)](+) proceeds via deprotonation of [Ru(η(2)-H(2))](+) to DHB complex, formation of hydrogen bond with Ru atom and subsequent proton transfer to the metal site.

  2. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D.; Krische, Michael J.

    2015-01-01

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo- and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k and 6m, respectively. Primary alcohols 2a, 2l and 2p were converted to the siloxy-crotylation products 3a, 3l and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes. PMID:26418572

  3. Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer.

    Science.gov (United States)

    Dub, Pavel A; Filippov, Oleg A; Belkova, Natalia V; Daran, Jean-Claude; Epstein, Lina M; Poli, Rinaldo; Shubina, Elena S

    2010-02-28

    The interaction of the carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H with Brønsted (fluorinated alcohols, (CF(3))(n)CH(3-n)OH (n = 1-3), and CF(3)COOH) and Lewis (Hg(C(6)F(5))(2), BF(3).OEt(2)) acids was studied by variable temperature IR and NMR ((1)H, (31)P, (13)C) spectroscopies in combination with DFT/B3LYP calculations. Among the two functionalities potentially capable of the interaction - carbonyl and hydride ligands - the first was found to be the preferential binding site for weak acids, yielding CO...HOR or CO...Hg complexes as well as CO...(HOR)(2) adducts. For stronger proton donors ((CF(3))(3)COH, CF(3)COOH) hydrogen-bonding to the hydride ligand can be revealed as an intermediate of the proton transfer reaction. Whereas proton transfer to the CO ligand is not feasible, protonation of the hydride ligand yields an (eta(2)-H(2)) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound [Cp*Mo(PMe(3))(3)(CO)](+)[(CF(3))(3)CO.2HOC(CF(3))(3)](-) resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF(3).OEt(2) was found to produce [Cp*Mo(PMe(3))(2)(CO)BF(4)] via initial attack of the hydride ligand.

  4. Cross-Species Analysis of Protein Dynamics Associated with Hydride and Proton Transfer in the Catalytic Cycle of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase.

    Science.gov (United States)

    Hoeven, Robin; Hardman, Samantha J O; Heyes, Derren J; Scrutton, Nigel S

    2016-02-16

    Experimental interrogation of the relationship between protein dynamics and enzyme catalysis is challenging. Light-activated protochlorophyllide oxidoreductase (POR) is an excellent model for investigating this relationship because photoinitiation of the reaction cycle enables coordinated turnover in a "dark-assembled" ternary enzyme-substrate complex. The catalytic cycle involves sequential hydride and proton transfers (from NADPH and an active site tyrosine residue, respectively) to the substrate protochlorophyllide. Studies with a limited cross-species subset of POR enzymes (n = 4) have suggested that protein dynamics associated with hydride and proton transfer are distinct [Heyes, D. J., Levy, C., Sakuma, M., Robertson, D. L., and Scrutton, N. S. (2011) J. Biol. Chem. 286, 11849-11854]. Here, we use steady-state assays and single-turnover laser flash spectroscopy to analyze hydride and proton transfer dynamics in an extended series of POR enzymes taken from many species, including cyanobacteria, algae, embryophytes, and angiosperms. Hydride/proton transfer in all eukaryotic PORs is faster compared to prokaryotic PORs, suggesting active site architecture has been optimized in eukaryotic PORs following endosymbiosis. Visible pump-probe spectroscopy was also used to demonstrate a common photoexcitation mechanism for representative POR enzymes from different branches of the phylogenetic tree. Dynamics associated with hydride transfer are localized to the active site of all POR enzymes and are conserved. However, dynamics associated with proton transfer are variable. Protein dynamics associated with proton transfer are also coupled to solvent dynamics in cyanobacterial PORs, and these networks are likely required to optimize (shorten) the donor-acceptor distance for proton transfer. These extended networks are absent in algal and plant PORs. Our analysis suggests that extended networks of dynamics are disfavored, possibly through natural selection. Implications for

  5. "Long-range" metal-ligand cooperation in H2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex.

    Science.gov (United States)

    Gunanathan, Chidambaram; Gnanaprakasam, Boopathy; Iron, Mark A; Shimon, Linda J W; Milstein, David

    2010-10-27

    The acridine-based pincer complex 1 exhibits an unprecedented mode of metal-ligand cooperation involving a "long-range" interaction between the distal acridine C9 position and the metal center. Reaction of 1 with H(2)/KOH results in H(2) splitting between the Ru center and C9 with concomitant dearomatization of the acridine moiety. DFT calculations show that this process involves the formation of a Ru dihydride intermediate bearing a bent acridine ligand in which C9 is in close proximity to a hydride ligand followed by through-space hydride transfer. Ammonia induces transfer of a hydride from the Ru center of 1 to C9 of the flexible acridine pincer ligand, forming an unusual dearomatized fac-acridine PNP complex.

  6. Recyclable Polystyrene-Supported Siloxane-Transfer Agent for Palladium-Catalyzed Cross-Coupling Reactions

    Science.gov (United States)

    2015-01-01

    The rational design, synthesis, and validation of a significantly improved insoluble polymer-supported siloxane-transfer agent has been achieved that permits efficient palladium-catalyzed cross-coupling reactions. The cross-linked polystyrene support facilitates product purification with excellent siloxane recycling. Drawbacks of a previous polymer-supported siloxane-transfer agent, relating to reaction efficiency and polymer stability after repeated cycles, have been addressed. PMID:24661113

  7. Rh-Catalyzed C–C Bond Cleavage by Transfer Hydroformylation

    Science.gov (United States)

    Murphy, Stephen K.; Park, Jung-Woo; Cruz, Faben A.; Dong, Vy M.

    2015-01-01

    The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rh(Xantphos)(benzoate) catalyst activates aldehyde C–H bonds with high chemoselectivity to trigger C–C bond cleavage and generate olefins at low loadings (0.3 to 2 mol%) and temperatures (22 to 80 °C). This mild protocol can be applied to various natural products and was used to achieve a three step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton-shuttle to enable transfer hydroformylation. PMID:25554782

  8. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

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

    Science.gov (United States)

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

    2009-01-07

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

  10. Enantioselective Brønsted acid catalyzed transfer hydrogenation: organocatalytic reduction of imines.

    Science.gov (United States)

    Rueping, Magnus; Sugiono, Erli; Azap, Cengiz; Theissmann, Thomas; Bolte, Michael

    2005-08-18

    The first enantioselective Brønsted acid catalyzed reduction of imines has been developed. This new organocatalytic transfer hydrogenation of ketimines with Hantzsch dihydropyridine as the hydrogen source offers a mild method to various chiral amines with high enantioselectivity. The stereochemistry of the chiral amines can be rationalized by a stereochemical model derived from an X-ray crystal structure of a chiral BINOL phosphate catalyst. [reaction: see text

  11. Peroxidase-catalyzed S-oxygenation: Mechanism of oxygen transfer for lactoperoxidase

    Energy Technology Data Exchange (ETDEWEB)

    Doerge, D.R.; Cooray, N.M. (Univ. of Hawaii, Honolulu (United States)); Brewster, M.E. (Pharmatec Inc., Alachua, FL (United States))

    1991-09-17

    The mechanism of organosulfur oxygenation by peroxidases (lactoperoxidase (LPX), chloroperoxidase, thyroid peroxidase, and horseradish peroxidase) and hydrogen peroxide was investigated by use of para-substituted thiobenzamides and thioanisoles. The rate constants for thiobenzamide oxygenation by LPX/H{sub 2}O{sub 2} were found to correlate with calculated vertical ionization potentials, suggesting rate-limiting single-electron transfer between LPX compound I and the organosulfur substrate. The incorporation of oxygen from {sup 18}O-labeled hydrogen peroxide, water, and molecular oxygen into sulfoxides during peroxidase-catalyzed S-oxygenation reactions was determined by LC- and GC-MS. All peroxidases tested catalyzed essentially quantitative oxygen transfer from {sup 18}O-labeled hydrogen peroxide into thiobenzamide S-oxide, suggesting that oxygen rebound from the oxoferryl heme is tightly coupled with the initial electron transfer in the active site. Experiments using H{sub 2}{sup 18}O{sub 2}, and H{sub 2}{sup 18}O showed the LPX catalyzed approximately 85,22, and 0% {sup 18}O-incorporation into thioanisole sulfoxide oxygen, respectively. These results are consistent with an active site controlled mechanism in which the protein radical form of LPX compound I is an intermediate in LPX-mediated sulfoxidation reactions.

  12. Steric Effect for Proton, Hydrogen-Atom, andHydride Transfer Reactions with Geometric Isomers of NADH-Model Ruthenium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fujita E.; Cohen, B.W.; Polyansky, D.E.; Achord, P.; Cabelli, D.; Muckerman, J.T.; Tanaka, K.; Thummel, R.P.; Zong, R.

    2012-01-01

    Two isomers, [Ru(1)]{sup 2+} (Ru = Ru(bpy){sub 2}, bpy = 2,2{prime}-bipyridine, 1 = 2-(pyrid-2{prime}-yl)-1-azaacridine) and [Ru(2)]{sup 2+} (2 = 3-(pyrid-2{prime}-yl)-4-azaacridine), are bio-inspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C{sub 1} complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]{sup 2+} and [Ru(2)]{sup 2+} have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]{sup 2+} and [Ru(2HH)]{sup 2+}, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2{sup {sm_bullet}-})]{sup +} in aprotic and even protic media is slow compared to that of [Ru(1{sup {sm_bullet}-})]{sup +}. The net hydrogen-atom transfer between *[Ru(1)]{sup 2+} and hydroquinone (H{sub 2}Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]{sup 2+} because the non-coordinated N atom is not easily available for an interaction with H{sub 2}Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]{sup 2+} to [Ph{sub 3}C]{sup +} is significantly slower than that of [Ru(2HH)]{sup 2+} owing to steric congestion at the donor site.

  13. Oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives by nitrous oxide via selective oxygen atom transfer reactions: insights from quantum chemistry calculations.

    Science.gov (United States)

    Xie, Hujun; Liu, Chengcheng; Yuan, Ying; Zhou, Tao; Fan, Ting; Lei, Qunfang; Fang, Wenjun

    2016-01-21

    The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp* = η(5)-C5Me5) by nitrous oxide via selective oxygen atom transfer reactions have been systematically studied by means of density functional theory (DFT) calculations. On the basis of the calculations, we investigated the original mechanism proposed by Hillhouse and co-workers for the activation of N2O. The calculations showed that the complex with an initial O-coordination of N2O to the coordinatively unsaturated Hf center is not a local minimum. Then we proposed a new reaction mechanism to investigate how N2O is activated and why N2O selectively oxidize phenyl and hydride ligands of . Frontier molecular orbital theory analysis indicates that N2O is activated by nucleophilic attack by the phenyl or hydride ligand. Present calculations provide new insights into the activation of N2O involving the direct oxygen atom transfer from nitrous oxide to metal-ligand bonds instead of the generally observed oxygen abstraction reaction to generate metal-oxo species.

  14. Non-oxidative coupling reaction of methane to ethane and hydrogen catalyzed by the silica-supported tantalum hydride: ([triple bond]SiO)2Ta-H.

    Science.gov (United States)

    Soulivong, Daravong; Norsic, Sébastien; Taoufik, Mostafa; Copéret, Christophe; Thivolle-Cazat, Jean; Chakka, Sudhakar; Basset, Jean-Marie

    2008-04-16

    Silica-supported tantalum hydride, (SiO)2Ta-H (1), proves to be the first single-site catalyst for the direct non-oxidative coupling transformation of methane into ethane and hydrogen at moderate temperatures, with a high selectivity (>98%). The reaction likely involves the tantalum-methyl-methylidene species as a key intermediate, where the methyl ligand can migrate onto the tantalum-methylidene affording the tantalum-ethyl.

  15. A role of proton transfer in peroxidase-catalyzed process elucidated by substrates docking calculations

    Directory of Open Access Journals (Sweden)

    Ziemys Arturas

    2001-08-01

    Full Text Available Abstract Background Previous kinetic investigations of fungal-peroxidase catalyzed oxidation of N-aryl hydroxamic acids (AHAs and N-aryl-N-hydroxy urethanes (AHUs revealed that the rate of reaction was independent of the formal redox potential of substrates. Moreover, the oxidation rate was 3–5 orders of magnitude less than for oxidation of physiological phenol substrates, though the redox potential was similar. Results To explain the unexpectedly low reactivity of AHAs and AHUs we made ab initio calculations of the molecular structure of the substrates following in silico docking in the active center of the enzyme. Conclusions AHAs and AHUs were docked at the distal side of heme in the sites formed by hydrophobic amino acid residues that retarded a proton transfer and finally the oxidation rate. The analogous phenol substrates were docked at different sites permitting fast proton transfer in the relay of distal His and water that helped fast substrate oxidation.

  16. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun

    2012-08-01

    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  17. On Transition Structures for Hydride Transfer Step in Enzyme Catalysis. A Comparative Study on Models of Glutathione Reductase Derived from Semiempirical, HF, and DFT Methods.

    Science.gov (United States)

    Andrés, Juan; Moliner, Vicente; Safont, Vicent S.; Domingo, Luís R.; Picher, María T.

    1996-11-01

    As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling.

  18. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations

    OpenAIRE

    2016-01-01

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD), than in H-tunneling. In order to examine the isoto...

  19. Thermodynamic Hydricity of Transition Metal Hydrides.

    Science.gov (United States)

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H(-)). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.

  20. Ag-catalyzed InAs nanowires grown on transferable graphite flakes

    Science.gov (United States)

    Meyer-Holdt, Jakob; Kanne, Thomas; Sestoft, Joachim E.; Gejl, Aske; Zeng, Lunjie; Johnson, Erik; Olsson, Eva; Nygård, Jesper; Krogstrup, Peter

    2016-09-01

    Semiconducting nanowires grown by quasi-van-der-Waals epitaxy on graphite flakes are a new class of hybrid materials that hold promise for scalable nanostructured devices within opto-electronics. Here we report on high aspect ratio and stacking fault free Ag-seeded InAs nanowires grown on exfoliated graphite flakes by molecular beam epitaxy. Ag catalyzes the InAs nanowire growth selectively on the graphite flakes and not on the underlying InAs substrates. This allows for easy transfer of the flexible graphite flakes with as-grown nanowire ensembles to arbitrary substrates by a micro-needle manipulator. Besides the possibilities for fabricating novel nanostructure device designs, we show how this method is used to study the parasitic growth and bicrystal match between the graphite flake and the nanowires by transmission electron microscopy.

  1. RecQ Helicase-catalyzed DNA Unwinding Detected by Fluorescence Resonance Energy Transfer

    Institute of Scientific and Technical Information of China (English)

    Xing-Dong ZHANG; Shuo-Xing DOU; Ping XIE; Peng-Ye WANG; Xu Guang XI

    2005-01-01

    A fluorometric assay was used to study the DNA unwinding kinetics induced by Escherichia coli RecQ helicase. This assay was based on fluorescence resonance energy transfer and carried out on stopped-flow, in which DNA unwinding was monitored by fluorescence emission enhancement of fluorescein resulting from helicase-catalyzed DNA unwinding. By this method, we determined the DNA unwinding rate of RecQ at different enzyme concentrations. We also studied the dependences of DNA unwinding magnitude and rate on magnesium ion concentration. We showed that this method could be used to determine the polarity of DNA unwinding. This assay should greatly facilitate further study of the mechanism for RecQcatalyzed DNA unwinding.

  2. Activity-stability relationships revisited in blue oxidases catalyzing electron transfer at extreme temperatures.

    Science.gov (United States)

    Roulling, Frédéric; Godin, Amandine; Cipolla, Alexandre; Collins, Tony; Miyazaki, Kentaro; Feller, Georges

    2016-09-01

    Cuproxidases are a subset of the blue multicopper oxidases that catalyze the oxidation of toxic Cu(I) ions into less harmful Cu(II) in the bacterial periplasm. Cuproxidases from psychrophilic, mesophilic, and thermophilic bacteria display the canonical features of temperature adaptation, such as increases in structural stability and apparent optimal temperature for activity with environmental temperature as well as increases in the binding affinity for catalytic and substrate copper ions. In contrast, the oxidative activities at 25 °C for both the psychrophilic and thermophilic enzymes are similar, suggesting that the nearly temperature-independent electron transfer rate does not require peculiar adjustments. Furthermore, the structural flexibilities of both the psychrophilic and thermophilic enzymes are also similar, indicating that the firm and precise bindings of the four catalytic copper ions are essential for the oxidase function. These results show that the requirements for enzymatic electron transfer, in the absence of the selective pressure of temperature on electron transfer rates, produce a specific adaptive pattern, which is distinct from that observed in enzymes possessing a well-defined active site and relying on conformational changes such as for the induced fit mechanism.

  3. Fluorobenzo[a]pyrenes as probes of the mechanism of cytochrome P450-catalyzed oxygen transfer in aromatic oxygenations

    NARCIS (Netherlands)

    Mulder, P.P.J.; Devanesan, P.; Alem, van K.; Lodder, G.; Rogan, E.G.; Cavalieri, E.L.

    2003-01-01

    Fluoro substitution of benzo[a]pyrene (BP) has been very useful in determining the mechanism of cytochrome P450-catalyzed oxygen transfer in the formation of 6-hydroxyBP (6-OHBP) and its resulting BP 1,6-, 3,6-, and 6,12-diones. We report here the metabolism of 1-FBP and 3-FBP, and PM3 calculations

  4. Ruthenium-catalyzed C-C coupling of fluorinated alcohols with allenes: dehydrogenation at the energetic limit of β-hydride elimination.

    Science.gov (United States)

    Sam, Brannon; Luong, Tom; Krische, Michael J

    2015-04-27

    Ruthenium(II) complexes catalyze the CC coupling of 1,1-disubstituted allenes and fluorinated alcohols to form homoallylic alcohols bearing all-carbon quaternary centers with good to complete levels of diastereoselectivity. Whereas fluorinated alcohols are relatively abundant and tractable, the corresponding aldehydes are often not commercially available because of their instability.

  5. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles.

    Science.gov (United States)

    Dumitrescu, Ioana; Crooks, Richard M

    2012-07-17

    Here we report on the effect of the mass transfer rate (k(t)) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt(147) and Pt(55)). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high k(t) conditions with simultaneous detection of H(2)O(2). At low k(t) (0.02 to 0.12 cm s(-1)) the effective number of electrons involved in ORR, n(eff), is 3.7 for Pt(147) and 3.4 for Pt(55). As k(t) is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H(2)O(2) detected remains constant, such that n(eff) barely changes over the entire k(t) range explored (0.02 cm s(-1)). This suggests that mass transfer does not affect n(eff), which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in n(eff) for the two sizes of Pt DENs (n(eff) = 3.7 and 3.5 for Pt(147) and Pt(55), respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect.

  6. Light-induced ruthenium-catalyzed nitrene transfer reactions: a photochemical approach towards N-acyl sulfimides and sulfoximines.

    Science.gov (United States)

    Bizet, Vincent; Buglioni, Laura; Bolm, Carsten

    2014-05-26

    1,4,2-Dioxazol-5-ones are five-membered heterocycles known to decarboxylate under thermal or photochemical conditions, thus yielding N-acyl nitrenes. Described herein is a light-induced ruthenium-catalyzed N-acyl nitrene transfer to sulfides and sulfoxides by decarboxylation of 1,4,2-dioxazol-5-ones at room temperature, thus providing direct access to N-acyl sulfimides and sulfoximines under mild reaction conditions. In addition, a one-pot sulfur imidation/oxidation sequence catalyzed by a single ruthenium complex is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Research on Metal Hydride Compressor System

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Ti-Zr series Laves phase hydrogen storage alloys with good hydrogen storage properties, such as large hydrogen capacity, rapid hydriding and dehydriding rate, high compression ratio, gentle plateau, small hysteresis, easily being activated and long cyclic stability etc. for metal hydride compressor have been investigated. In addition, a hydride compressor with special characteristics, namely, advanced filling method, good heat transfer effect and reasonable structural design etc. has also been constructed. A hydride compressor cryogenic system has been assembled coupling the compressor with a J-T micro-throttling refrigeration device and its cooling capacity can reach 0.4 W at 25 K.

  8. Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine

    Institute of Scientific and Technical Information of China (English)

    LI; Ming; ZHENG; Wenxu

    2006-01-01

    The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this reaction are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.

  9. Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

    Science.gov (United States)

    Petra; Kamer; Spek; Schoemaker; van Leeuwen PW

    2000-05-19

    A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.

  10. Photochemistry of Transition Metal Hydrides.

    Science.gov (United States)

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

    Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

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

    KAUST Repository

    He, Lipeng

    2012-03-01

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

  12. Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

    Science.gov (United States)

    Pappas, Iraklis; Chirik, Paul J

    2016-10-03

    The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η(5)-C5Me5)(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η(5)-C5R5)(CO)3Cr-H ([Cr](R)-H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH3 by proton coupled electron transfer at a well-defined transition metal center.

  13. Boron Hydrides

    Science.gov (United States)

    1946-07-01

    of direct interest could be b.P.4d. ’Thus the discovory of a now proj.ect, since silano is probably too readily infla-zmablo for practical usc’ this...devoted, ho specc4fie compounds vhitih a’-ould be tocdte at prescnt arc: nron tiy * silano , %;2.SiFi3 , diothyl sila~no, (C2 115 )2 Si112, mono r.-rop; ! (n...Bcrohydrido or Li h.... I .A-4A- The prepuation of Silano med of Stannane by the interaction or lithium aluzirun hydride v-ithl silicon tetrtchiorido and

  14. Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2011-01-01

    Trialkylborane additives promote reduction of CO(2) to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO(2) to give a formate-borane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO(2) reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate-borane adduct.

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

    Indian Academy of Sciences (India)

    ARUN KUMAR PANDIA KUMAR; ASHOKA G SAMUELSON

    2016-09-01

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

  16. Influence of ultrasonic condition on phase transfer catalyzed radical polymerization of methyl methacrylate in two phase system - A kinetic study.

    Science.gov (United States)

    Marimuthu, Elumalai; Murugesan, Vajjiravel

    2017-09-01

    An ultrasonic condition assisted phase transfer catalyzed radical polymerization of methyl methacrylate was investigated in an ethyl acetate/water two phase system at 60±1°C and 25kHz, 300W under inert atmosphere. The influence of monomer, initiator, catalyst and temperature, volume fraction of aqueous phase on the rate of polymerization was examined in detail. The reaction order was found to be unity for monomer, initiator and catalyst. Generally, the reaction rate was relatively fast in two phase system, when a catalytic amount of phase transfer catalyst was used. The combined approach, use of ultrasonic and PTC condition was significantly enhances the rate of polymerization. An ultrasonic and phase transfer catalyzed radical polymerization of methyl methacrylate has shown about three fold enhancements in the rate compared with silent polymerization of MMA using cetyltrimethylammonium bromide as PTC. The resultant kinetics was evaluated with silent polymerization and an important feature was discussed. The activation energy and other thermodynamic parameters were computed. Based on the obtained results an appropriate radical mechanism has been derived. TGA showed the polymer was stable up to 150°C. The FT-IR and DSC analysis validates the atactic nature of the obtained polymer. The XRD pattern reveals the amorphous nature of polymer was dominated. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illus trated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the cata lyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane ad duct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads to R-chiral alcohols.

  18. Hydride heat pump with heat regenerator

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative hydride heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system. A series of at least four canisters containing a lower temperature performing hydride and a series of at least four canisters containing a higher temperature performing hydride is provided. Each canister contains a heat conductive passageway through which a heat transfer fluid is circulated so that sensible heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  19. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-01-01

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, cold,'' process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility's metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  20. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-12-31

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, ``cold,`` process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility`s metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

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

    Science.gov (United States)

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

    2012-12-01

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

  2. Selective ruthenium-catalyzed transfer hydrogenations of nitriles to amines with 2-butanol.

    Science.gov (United States)

    Werkmeister, Svenja; Bornschein, Christoph; Junge, Kathrin; Beller, Matthias

    2013-04-02

    Transfer your hydrogen: Fast and general transfer hydrogenation of nitriles to form primary amines is possible with a homogeneous Ru/1,4-bis(diphenylphosphino)butane (DPPB) catalyst (see scheme). The use of 2-butanol as the hydrogen-transfer reagent is essential for the selective reduction of aromatic, heteroaromatic, and aliphatic nitriles with this system. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Microbial activity catalyzes oxygen transfer in membrane-aerated nitritating biofilm reactors

    DEFF Research Database (Denmark)

    Pellicer i Nàcher, Carles; Domingo Felez, Carlos; Lackner, Susanne

    2013-01-01

    of the liquid boundary layer developed at the membrane-liquid interface during clean water tests accounted for two thirds of the total mass transfer resistance, suggesting a strong underestimation of the oxygen transfer rates when it is absent (e.g. after biofilm growth). Reactor operation to attain partial...

  4. Numerical simulation and performance test of metal hydride hydrogen storage system

    Directory of Open Access Journals (Sweden)

    Tzu-Hsiang Yen, Bin-Hao Chen, Bao-Dong Chen

    2011-05-01

    Full Text Available Metal hydride reactors are widely used in many industrial applications, such as hydrogen storage, thermal compression, heat pump, etc. According to the research requirement of metal hydride hydrogen storage, the thermal analyses have been implemented in the paper. The metal hydride reaction beds are considered as coupled cylindrical tube modules which combine the chemical absorption and desorption in metal hydride. The model is then used metal hydride LaNi5 as an example to predict the performance of metal hydride hydrogen storage devices, such as the position of hydration front and the thermal flux. Under the different boundary condition the characteristics of heat transfer and mass transfer in metal hydride have influence on the hydrogen absorption and desorption. The researches revealed that the scroll design can improve the temperature distribution in the reactor and the porous tube for directing hydrogen can increase the penetration depth of hydride reaction to decrease the hydrogen absorption time.

  5. Rhodium-catalyzed acyl-transfer reaction between benzyl ketones and thioesters: synthesis of unsymmetric ketones by ketone CO-C bond cleavage and intermolecular rearrangement.

    Science.gov (United States)

    Arisawa, Mieko; Kuwajima, Manabu; Toriyama, Fumihiko; Li, Guangzhe; Yamaguchi, Masahiko

    2012-07-20

    In the presence of catalytic amounts of RhH(CO)(PPh3)3 and 1,2-bis(diphenylphosphino)benzene (dppBz), acyl groups were transferred between benzyl ketones and thioesters/aryl esters. The rhodium complex catalyzed the cleavage of ketone CO-C bonds and intermolecular rearrangement giving unsymmetric ketones. The acyl-transfer reaction also occurred with 1-(p-chlorophenyl)-3-(p-cyanophenyl)propane-2-one giving unsymmetric ketones.

  6. Synthesis of ruthenium hydride

    Science.gov (United States)

    Kuzovnikov, M. A.; Tkacz, M.

    2016-02-01

    Ruthenium hydride was synthesized at a hydrogen pressure of about 14 GPa in a diamond-anvil cell. Energy-dispersive x-ray diffraction was used to monitor the ruthenium crystal structure as a function of hydrogen pressure up to 30 GPa. The hydride formation was accompanied by phase transition from the original hcp structure of the pristine metal to the fcc structure. Our results confirmed the theoretical prediction of ruthenium hydride formation under hydrogen pressure. The standard Gibbs free energy of the ruthenium hydride formation reaction was calculated assuming the pressure of decomposition as the equilibrium pressure.

  7. A highly enantioselective phase-transfer catalyzed epoxidation of enones with a mild oxidant, trichloroisocyanuric acid.

    Science.gov (United States)

    Ye, Jinxing; Wang, Yongcan; Liu, Renhua; Zhang, Guofu; Zhang, Qing; Chen, Jiping; Liang, Xinmiao

    2003-11-07

    The enantioselective epoxidation can be carried out using trichloroisocyanuric acid (TCCA) as oxidant in the presence of chiral quaternary ammonium salt as a phase-transfer catalyst; treatment of chalcone derivatives with TCCA under mild conditions afforded the corresponding epoxy ketones in good yields with moderate to excellent enantioselectivities of up to 96%.

  8. Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity

    Science.gov (United States)

    Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

    2016-01-01

    CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2. We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis. PMID:27450088

  9. Pd0-Catalyzed Methyl Transfer on Nucleosides and Oligonucleotides, Envisaged as a PET Tracer

    Directory of Open Access Journals (Sweden)

    Eric Fouquet

    2013-11-01

    Full Text Available The methyl transfer reaction from activated monomethyltin, via a modified Stille coupling reaction, was studied under “ligandless” conditions on fully deprotected 5'-modified nucleosides and one dinucleotide. The reaction was optimized to proceed in a few minutes and quantitative yield, even under dilute conditions, thus affording a rapid and efficient new method for oligonucleotide labelling with carbon-11.

  10. Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

    Science.gov (United States)

    Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

    2017-08-30

    Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph3C][B(C6F5)4]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt2 reveal that ZnEt2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

  11. Mechanistic insights on N-heterocyclic carbene-catalyzed annulations: the role of base-assisted proton transfers.

    Science.gov (United States)

    Verma, Pragya; Patni, Priya A; Sunoj, Raghavan B

    2011-07-15

    The density functional theory investigation on the mechanism of NHC-catalyzed cycloannulation reaction of the homoenolate derived from butenal with pentenone is studied. The M06-2X/6-31+G** and B3LYP/6-31+G** levels of theory, including the effect of continuum solvation in dichloromethane and tetrahydrofuran, are employed. Several mechanistic scenarios are examined for each elementary step by identifying the key intermediates and the corresponding transition states interconnecting them on the respective potential energy surfaces. Both assisted and unassisted pathways for important proton transfer steps are considered, respectively, with and without the explicit inclusion of base (DBU) in the corresponding transition states. The barrier for the crucial proton transfer steps involved in the formation of the Breslow intermediate as well as in the subsequent steps is found to be significantly lowered by explicit inclusion of DBU. The energetic comparison between two key pathways, depicted as path A and path B, respectively, leading to cyclopentene and cyclopentanone derivatives, is performed. The major mechanistic bifurcation has been identified as emanating from the site of enolization of the initial zwitterionic intermediate resulting from the addition of a homoenolate equivalent to enone. If the enolization occurs nearer to the NHC moiety, the reaction is likely to proceed through path A, leading to cyclopentene. The enolization away from NHC leads to cyclopentanone product through path B. The computed results are generally in good agreement with the reported experimental results.

  12. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    Science.gov (United States)

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

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

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

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

  14. Phase Transfer Catalyzed Synthesis of Thiosemicarbazide Derivatives of 2-ethoxybenzoic Acid

    Institute of Scientific and Technical Information of China (English)

    WEI; TaiBao

    2001-01-01

    A series of 1,4-disubstitued thiosemicarbazides and their related heterocyclic compounds have been found to possess important biological activities[1]. Some thiosemicarbazides have been found to be useful as herbicides, insecticides and plant-growth regulators [1]. In view of these and in continuation of our earlier work on the synthesis and biological activity of thiosemicarbaides derivatives [2], we now report a convenient and efficient method for the preparation of thiosemicarbazides derivatives of 2-ethoxybenzoic acid under the condition of solid-liquid phase transfer catalysis using PEG-400 as the catalyst.  ……

  15. Phase Transfer Catalyzed Synthesis of Thiosemicarbazide Derivatives of 2-ethoxybenzoic Acid

    Institute of Scientific and Technical Information of China (English)

    WEI TaiBao; ZHANG YouMing; WU JiaWei

    2001-01-01

    @@ A series of 1,4-disubstitued thiosemicarbazides and their related heterocyclic compounds have been found to possess important biological activities[1]. Some thiosemicarbazides have been found to be useful as herbicides, insecticides and plant-growth regulators [1]. In view of these and in continuation of our earlier work on the synthesis and biological activity of thiosemicarbaides derivatives [2], we now report a convenient and efficient method for the preparation of thiosemicarbazides derivatives of 2-ethoxybenzoic acid under the condition of solid-liquid phase transfer catalysis using PEG-400 as the catalyst.

  16. Hysteresis in Metal Hydrides.

    Science.gov (United States)

    Flanagan, Ted B., And Others

    1987-01-01

    This paper describes a reproducible process where the irreversibility can be readily evaluated and provides a thermodynamic description of the important phenomenon of hysteresis. A metal hydride is used because hysteresis is observed during the formation and decomposition of the hydride phase. (RH)

  17. DNA strand transfer catalyzed by vaccinia topoisomerase: ligation of DNAs containing a 3' mononucleotide overhang.

    Science.gov (United States)

    Cheng, C; Shuman, S

    2000-05-01

    The specificity of vaccinia topoisomerase for transesterification to DNA at the sequence 5'-CCCTT and its versatility in strand transfer have illuminated the recombinogenic properties of type IB topoisomerases and spawned topoisomerase-based strategies for DNA cloning. Here we characterize a pathway of topoisomerase-mediated DNA ligation in which enzyme bound covalently to a CCCTT end with an unpaired +1T nucleotide rapidly and efficiently joins the CCCTT strand to a duplex DNA containing a 3' A overhang. The joining reaction occurs with high efficiency, albeit slowly, to duplex DNAs containing 3' G, T or C overhangs. Strand transfer can be restricted to the correctly paired 3' A overhang by including 0.5 M NaCl in the ligation reaction mixture. The effects of base mismatches and increased ionic strength on the rates of 3' overhang ligation provide a quantitative picture of the relative contributions of +1 T:A base pairing and electrostatic interactions downstream of the scissile phosphate to the productive binding of an unlinked acceptor DNA to the active site. The results clarify the biochemistry underlying topoisomerase-cloning of PCR products with non-templated 3' overhangs.

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

    Institute of Scientific and Technical Information of China (English)

    XUE Ping; WU Tao

    2007-01-01

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

  19. Propane dehydrogenation catalyzed by ZSM-5 zeolites. A mechanistic study based on the selective energy transfer (SET) theory.

    Science.gov (United States)

    Larsson, Ragnar

    2015-02-02

    Experimentally determined activation energies of propane dehydrogenation catalyzed by ZSM-5 zeolites have been used to test the SET theory. The basis of this theory is that the catalyst system transfers vibrational energy via a resonance process to a specific vibration mode of the reacting molecule. Being excited up to a certain number of vibrational quanta the molecule is brought to reaction. By analyzing the above-mentioned activation energies we found the wave number of this "specific mode" to be 1065 cm-1. This is very close to the rocking vibration of propane (1053 cm-1). We suggest that the propane molecule reacts when excited so that the CH3 group has been forced towards a flat structure with a carbon atom hybridization that is more sp2 than sp3. Consequently there is no way for three H-atoms to bind to the carbon and one of them must leave. This is the starting point of the reaction. The isokinetic temperature of the system was found as Tiso = 727 ± 4 K. From the SET formula for Tiso when both energy-donating (ω) and energy-accepting (ν) vibrations have the same frequency, viz., Tiso = Nhcν/2R, we obtain ν = ω = 1011 ± 6 cm-1. This agrees rather well with the CH3 rocking mode (1053 cm-1) and also with asymmetric "TO4" stretching vibrations of the zeolite structure (ω).

  20. Propane Dehydrogenation Catalyzed by ZSM-5 Zeolites. A Mechanistic Study Based on the Selective Energy Transfer (SET Theory

    Directory of Open Access Journals (Sweden)

    Ragnar Larsson

    2015-02-01

    Full Text Available Experimentally determined activation energies of propane dehydrogenation catalyzed by ZSM-5 zeolites have been used to test the SET theory. The basis of this theory is that the catalyst system transfers vibrational energy via a resonance process to a specific vibration mode of the reacting molecule. Being excited up to a certain number of vibrational quanta the molecule is brought to reaction. By analyzing the above-mentioned activation energies we found the wave number of this “specific mode” to be 1065 cm−1. This is very close to the rocking vibration of propane (1053 cm−1. We suggest that the propane molecule reacts when excited so that the CH3 group has been forced towards a flat structure with a carbon atom hybridization that is more sp2 than sp3. Consequently there is no way for three H-atoms to bind to the carbon and one of them must leave. This is the starting point of the reaction. The isokinetic temperature of the system was found as Tiso = 727 ± 4 K. From the SET formula for Tiso when both energy-donating (ω and energy-accepting (ν vibrations have the same frequency, viz., Tiso = Nhcν/2R, we obtain ν = ω = 1011 ± 6 cm−1. This agrees rather well with the CH3 rocking mode (1053 cm−1 and also with asymmetric “TO4” stretching vibrations of the zeolite structure (ω.

  1. Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.

    Science.gov (United States)

    Reiser, Oliver

    2016-09-20

    ) the tendency for ligand exchange in Cu(I)L2 assemblies allows the efficient synthesis of heteroleptic Cu(I)LL' complexes to tune the steric and electronic properties and also might coordinate and thus activate substrates in the course of a reaction in addition to electron transfer. Moreover, new photoredox cycles have also been discovered beyond the visible-light-induced Cu(I)* → Cu(II) electron transfer that is arguably best known: examples of the Cu(II)* → Cu(I) and Cu(I)* → Cu(0) transitions have been realized, greatly broadening the potential for copper-based photoredox-catalyzed transformations. Finally, a number of organic transformations that are unique to Cu(I) photoredox catalysts have been discovered.

  2. New insights into the mechanism of proton transfer to hydride complexes: kinetic and theoretical evidence showing the existence of competitive pathways for protonation of the cluster [W3S4H3(dmpe)3]+ with acids.

    Science.gov (United States)

    Algarra, Andrés G; Basallote, Manuel G; Feliz, Marta; Fernández-Trujillo, M Jesús; Llusar, Rosa; Safont, Vicent S

    2006-02-01

    The reaction of the hydride cluster [W3S4H3(dmpe)3]+ (1, dmpe = 1,2-bis(dimethylphosphanyl)ethane) with acids (HCl, CF3COOH, HBF4) in CH2Cl2 solution under pseudo-first-order conditions of excess acid occurs with three kinetically distinguishable steps that can be interpreted as corresponding to successive formal substitution processes of the coordinated hydrides by the anion of the acid (HCl, CF3COOH) or the solvent (HBF4). Whereas the rate law for the third step changes with the nature of the acid, the first two kinetic steps always show a second-order dependence on acid concentration. In contrast, a single kinetic step with a first-order dependence with respect to the acid is observed when the experiments are carried out with a deficit of acid. The decrease in the T1 values for the hydride NMR signal of 1 in the presence of added HCl suggests the formation of an adduct with a W-H...H-Cl dihydrogen bond. Theoretical calculations for the reaction with HCl indicate that the kinetic results in CH2Cl2 solution can be interpreted on the basis of a mechanism with two competitive pathways. One of the pathways consists of direct proton transfer within the W-H...H-Cl adduct to form W-Cl and H2, whereas the other requires the presence of a second HCl molecule to form a W-H...H-Cl...H-Cl adduct that transforms into W-Cl, H2 and HCl in the rate-determining step. The activation barriers and the structures of the transition states for both pathways were also calculated, and the results indicate that both pathways can be competitive and that the transition states can be described in both cases as a dihydrogen complex hydrogen-bonded to Cl- or HCl2(-).

  3. The role of solvent on the mechanism of proton transfer to hydride complexes: the case of the [W(3)PdS(4)H(3)(dmpe)(3)(CO)](+) cubane cluster.

    Science.gov (United States)

    Algarra, Andrés G; Basallote, Manuel G; Feliz, Marta; Fernández-Trujillo, M Jesús; Llusar, Rosa; Safont, Vicent S

    2010-02-01

    The kinetics of reaction of the [W(3)PdS(4)H(3)(dmpe)(3)(CO)](+) hydride cluster (1(+)) with HCl has been measured in dichloromethane, and a second-order dependence with respect to the acid is found for the initial step. In the presence of added BF(4) (-) the second-order dependence is maintained, but there is a deceleration that becomes more evident as the acid concentration increases. DFT calculations indicate that these results can be rationalized on the basis of the mechanism previously proposed for the same reaction of the closely related [W(3)S(4)H(3)(dmpe)(3)](+) cluster, which involves parallel first- and second-order pathways in which the coordinated hydride interacts with one and two acid molecules, and ion pairing to BF(4) (-) hinders formation of dihydrogen bonded adducts able to evolve to the products of proton transfer. Additional DFT calculations are reported to understand the behavior of the cluster in neat acetonitrile and acetonitrile-water mixtures. The interaction of the HCl molecule with CH(3)CN is stronger than the W-H...HCl dihydrogen bond and so the reaction pathways operating in dichloromethane become inefficient, in agreement with the lack of reaction between 1(+) and HCl in neat acetonitrile. However, the attacking species in acetonitrile-water mixtures is the solvated proton, and DFT calculations indicate that the reaction can then go through pathways involving solvent attack to the W centers, while still maintaining the coordinated hydride, which is made possible by the capability of the cluster to undergo structural changes in its core.

  4. Asymmetric phase-transfer-catalyzed conjugate addition of glycine imine to exocyclic α,β-unsaturated ketones: construction of polycyclic imines containing three stereocenters.

    Science.gov (United States)

    Nie, Jing; Hua, Ming-Qing; Xiong, Heng-Ying; Zheng, Yan; Ma, Jun-An

    2012-05-04

    We developed a facile, one-pot, multistep transformation between glycine imine and exocyclic α,β-unsaturated ketones in reactions catalyzed by chiral phase-transfer catalysts (PTC). A series of polycyclic imines containing three adjacent stereocenters were obtained in good to high yields with high diastereo- and enantioselectivities. Further transformation of the imines could afford N-fused polycyclic compounds with four adjacent stereocenters.

  5. Escherichia coli DNA helicase I catalyzes a sequence-specific cleavage/ligation reaction at the F plasmid origin of transfer.

    Science.gov (United States)

    Sherman, J A; Matson, S W

    1994-10-21

    Recent studies have shown that the Escherichia coli F plasmid-encoded traI gene product (TraIp), also known as DNA helicase I, catalyzes the formation of the site- and strand-specific nick that initiates F plasmid DNA transfer. Scission of the phosphodiester bond at the nic site within the origin of transfer (oriT) is accompanied by the covalent attachment of TraIp to the 5'-phosphate of the nicked DNA strand. This mechanism suggests that TraIp may also be capable of catalyzing a DNA ligation reaction using the energy stored in the protein-DNA intermediate. To test this possibility, an in vitro assay was designed that utilized short single-stranded DNA oligonucleotides of different lengths derived from the region within oriT that spanned the nic site. Purified TraIp was capable of efficiently cleaving single-stranded DNA that contained a nic site, and upon cleavage, the protein became covalently linked to the 5'-end of the nic site. When TraIp was incubated with two oligonucleotides of different length that contained the nic site, there was formation of novel recombinant products resulting from a TraIp-catalyzed cleavage/ligation reaction. Furthermore, the cleavage and ligation reactions were both sequence-specific. These data suggest that TraIp plays an important role in the initiation and termination of conjugative DNA transfer.

  6. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  7. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  8. Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction.

    Science.gov (United States)

    Li, Ji-Lai; Mata, Ricardo A; Ryde, Ulf

    2013-03-12

    The oxygen-atom transfer reaction catalyzed by the mononuclear molybdenum enzyme dimethyl sulfoxide reductase (DMSOR) has attracted considerable attention through both experimental and theoretical studies. We show here that this reaction is more sensitive to details of quantum mechanical calculations than what has previously been appreciated. Basis sets of at least triple-ζ quality are needed to obtain qualitatively correct results. Dispersion has an appreciable effect on the reaction, in particular the binding of the substrate or the dissociation of the product (up to 34 kJ/mol). Polar and nonpolar solvation effects are also significant, especially if the enzyme can avoid cavitation effects by using a preformed active-site cavity. Relativistic effects are considerable (up to 22 kJ/mol), but they are reasonably well treated by a relativistic effective core potential. Various density-functional methods give widely different results for the activation and reaction energy (differences of over 100 kJ/mol), mainly reflecting the amount of exact exchange in the functional, owing to the oxidation of Mo from +IV to +VI. By calibration toward local CCSD(T0) calculations, we show that none of eight tested functionals (TPSS, BP86, BLYP, B97-D, TPSSH, B3LYP, PBE0, and BHLYP) give accurate energies for all states in the reaction. Instead, B3LYP gives the best activation barrier, whereas pure functionals give more accurate energies for the other states. Our best results indicate that the enzyme follows a two-step associative reaction mechanism with an overall activation enthalpy of 63 kJ/mol, which is in excellent agreement with the experimental results.

  9. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    current. For applications involving the utilisation of high currents, the activation to the required level could be as high as 100 cycles, whereas for low current applications, 5-10 activation cycles could be sufficient when the same current was used for the activation (pretreatment of the alloy might enhance the activation considerably). When an electrode made of an alloy with a relatively high hydrogen equilibrium (plateau) pressure was cycled under a moderate external inert gas pressure, a new activation process was observed when the pressure was increased. This indicated that the activated state was dependent on several factors, which indicated the need of examining each factor individually as well as combined in order to gain a complete understanding of the process. The characterization of metal hydride electrodes by means of electrochemical impedance spectroscopy, showed that this technique when used properly and in combination with other characterization techniques can be very useful in determining the significance of the different sub-processes in the overall process. The impedance response for different laboratory metal hydride electrodes were successfully modelled and fitted to experimental data for both AB{sub 5} type alloys and a MgNi type electrode. The following sub processes were found to be significant for the overall reaction rate: charge transfer resistance, double layer capacitance and impedance resulting from hydrogen diffusion within the metal lattice. The diffusion process was best modelled when using a spherical diffusion geometry. To fit the experimental data, equations describing the current distribution in porous electrodes were required. To account for possible parallel hydrogen evolution during charging, it was necessary to include this step in the model for electrodes having a more negative open circuit potential than the reversible hydrogen evolution potential. Indications of one or more parallel reduction/oxidation processes competing with

  10. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    current. For applications involving the utilisation of high currents, the activation to the required level could be as high as 100 cycles, whereas for low current applications, 5-10 activation cycles could be sufficient when the same current was used for the activation (pretreatment of the alloy might enhance the activation considerably). When an electrode made of an alloy with a relatively high hydrogen equilibrium (plateau) pressure was cycled under a moderate external inert gas pressure, a new activation process was observed when the pressure was increased. This indicated that the activated state was dependent on several factors, which indicated the need of examining each factor individually as well as combined in order to gain a complete understanding of the process. The characterization of metal hydride electrodes by means of electrochemical impedance spectroscopy, showed that this technique when used properly and in combination with other characterization techniques can be very useful in determining the significance of the different sub-processes in the overall process. The impedance response for different laboratory metal hydride electrodes were successfully modelled and fitted to experimental data for both AB{sub 5} type alloys and a MgNi type electrode. The following sub processes were found to be significant for the overall reaction rate: charge transfer resistance, double layer capacitance and impedance resulting from hydrogen diffusion within the metal lattice. The diffusion process was best modelled when using a spherical diffusion geometry. To fit the experimental data, equations describing the current distribution in porous electrodes were required. To account for possible parallel hydrogen evolution during charging, it was necessary to include this step in the model for electrodes having a more negative open circuit potential than the reversible hydrogen evolution potential. Indications of one or more parallel reduction/oxidation processes competing with

  11. Metal hydrides based high energy density thermal battery

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zhigang Zak, E-mail: zak.fang@utah.edu [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Zhou, Chengshang; Fan, Peng [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Udell, Kent S. [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States); Bowman, Robert C. [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Vajo, John J.; Purewal, Justin J. [HRL Laboratories, LLC, 3011 Malibu Canyon Road, Malibu, CA 90265 (United States); Kekelia, Bidzina [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States)

    2015-10-05

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH{sub 2} and TiMnV as a working pair. • High energy density can be achieved by the use of MgH{sub 2} to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH{sub 2} as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV{sub 0.62}Mn{sub 1.5} alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles.

  12. ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jy-An John [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Yan, Yong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Wang, Hong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-10-28

    A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydrides in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation tests of

  13. Lightweight hydride storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W. [Sandia National Labs., Livermore, CA (United States)

    1995-09-01

    The need for lightweight hydrides in vehicular applications has prompted considerable research into the use of magnesium and its alloys. Although this earlier work has provided some improved performance in operating temperature and pressure, substantial improvements are needed before these materials will significantly enhance the performance of an engineered system on a vehicle. We are extending the work of previous investigators on Mg alloys to reduce the operating temperature and hydride heat of formation in light weight materials. Two important results will be discussed in this paper: (1) a promising new alloy hydride was found which has better pressure-temperature characteristics than any previous Mg alloy and, (2) a new fabrication process for existing Mg alloys was developed and demonstrated. The new alloy hydride is composed of magnesium, aluminum and nickel. It has an equilibrium hydrogen overpressure of 1.3 atm. at 200{degrees}C and a storage capacity between 3 and 4 wt.% hydrogen. A hydrogen release rate of approximately 5 x 10{sup -4} moles-H{sub 2}/gm-min was measured at 200{degrees}C. The hydride heat of formation was found to be 13.5 - 14 kcal/mole-H{sub 2}, somewhat lower than Mg{sub 2}Ni. The new fabrication method takes advantage of the high vapor transport of magnesium. It was found that Mg{sub 2}Ni produced by our low temperature process was better than conventional materials because it was single phase (no Mg phase) and could be fabricated with very small particle sizes. Hydride measurements on this material showed faster kinetic response than conventional material. The technique could potentially be applied to in-situ hydride bed fabrication with improved packing density, release kinetics, thermal properties and mechanical stability.

  14. Effect of osmolytes on protein dynamics in the lactate dehydrogenase-catalyzed reaction.

    Science.gov (United States)

    Zhadin, Nickolay; Callender, Robert

    2011-03-15

    Laser-induced temperature jump relaxation spectroscopy was used to probe the effect of osmolytes on the microscopic rate constants of the lactate dehydrogenase-catalyzed reaction. NADH fluorescence and absorption relaxation kinetics were measured for the lactate dehydrogenase (LDH) reaction system in the presence of varying amounts of trimethylamine N-oxide (TMAO), a protein-stabilizing osmolyte, or urea, a protein-destabilizing osmolyte. Trimethylamine N-oxide (TMAO) at a concentration of 1 M strongly increases the rate of hydride transfer, nearly nullifies its activation energy, and also slightly increases the enthalpy of hydride transfer. In 1 M urea, the hydride transfer enthalpy is almost nullified, but the activation energy of the step is not affected significantly. TMAO increases the preference of the closed conformation of the active site loop in the LDH·NAD(+)·lactate complex; urea decreases it. The loop opening rate in the LDH·NADH·pyruvate complex changes its temperature dependence to inverse Arrhenius with TMAO. In this complex, urea accelerates the loop motion, without changing the loop opening enthalpy. A strong, non-Arrhenius decrease in the pyruvate binding rate in the presence of TMAO offers a decrease in the fraction of the open loop, pyruvate binding competent form at higher temperatures. The pyruvate off rate is not affected by urea but decreases with TMAO. Thus, the osmolytes strongly affect the rates and thermodynamics of specific events along the LDH-catalyzed reaction: binding of substrates, loop closure, and the chemical event. Qualitatively, these results can be understood as an osmolyte-induced change in the energy landscape of the protein complexes, shifting the conformational nature of functional substates within the protein ensemble.

  15. Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

    KAUST Repository

    Werghi, Baraa

    2016-09-26

    The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

  16. Hydrogen, lithium, and lithium hydride production

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

    2017-06-20

    A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

  17. Mechanistic studies of Wacker-type amidocyclization of alkenes catalyzed by (IMes)Pd(TFA)2(H2O): kinetic and stereochemical implications of proton transfer.

    Science.gov (United States)

    Ye, Xuan; White, Paul B; Stahl, Shannon S

    2013-03-01

    The stereochemical course of the amidopalladation of alkenes has important implications for the development of enantioselective Pd-catalyzed "Wacker-type" oxidative amidation of alkenes. We have recently shown that the addition of base (Na2CO3) can alter the stereochemical course of amidopalladation in the (IMes)Pd(TFA)2(H2O)-catalyzed aerobic oxidative amidation of alkene. In this study, the mechanism of (IMes)Pd(TFA)2(H2O)-catalyzed oxidative heterocyclization of (Z)-4-hexenyltosylamide was investigated in the presence and absence of exogenous base Na2CO3. The results reveal two parallel pathways in the absence of base: a cis-amidopalladation pathway with turnover-limiting deprotonation of the sulfonamide nucleophile and a trans-amidopalladation pathway with turnover-limiting nucleophilic attack of sulfonamide on the coordinated alkene. The addition of base (Na2CO3) lowers the energy barrier associated with the proton transfer, leading to an overall faster turnover rate and exclusive cis-amidopalladation of alkene.

  18. Enhancement in dehydriding performance of magnesium hydride by iron incorporation: A combined experimental and theoretical investigation

    Science.gov (United States)

    Chen, Haipeng; Yu, Hao; Zhang, Qianqian; Liu, Bogu; Liu, Pei; Zhou, Xinpei; Han, Zongying; Zhou, Shixue

    2016-08-01

    Structural change and dehydriding mechanism of MgH2 with atomic Fe incorporation from reactive ball milling are characterized and simulated by first-principles calculation. Two kinds of hydrides β- and γ-MgH2 are formed from Mg powders under hydrogen atmosphere by 3.0 h of milling with pretreated anthracite as milling aid. Experimental studies suggest that the atomic Fe can be incorporated onto MgH2 surface by the shearing effect of Fe-based milling balls on Mg/MgH2 particles. The incorporated Fe has a high dispersity on MgH2 surface and can form atomic clusters FeH4/FeH2 by combining with H anions. The dehydriding reaction of the Fe-incorporated MgH2 begins at hydride surface and shows an enhanced performance with apparent activation energy of 110.3 kJ mol-1. Theoretical studies suggest that the incorporated Fe can act as a bridge that contributes to electron transfer from H anion to Mg cation before H2 molecule formation. The intrinsic reason of atomic Fe in catalyzing dehydriding reaction of MgH2 lies in its moderate strength of electron attraction.

  19. Novel fuel cell stack with coupled metal hydride containers

    Science.gov (United States)

    Liu, Zhixiang; Li, Yan; Bu, Qingyuan; Guzy, Christopher J.; Li, Qi; Chen, Weirong; Wang, Cheng

    2016-10-01

    Air-cooled, self-humidifying hydrogen fuel cells are often used for backup and portable power sources, with a metal hydride used as the hydrogen storage material. To provide a stable hydrogen flow to the fuel cell stack, heat must be provided to the metal hydride. Conventionally, the heat released from the exothermic reaction of hydrogen and oxygen in the fuel cell stack to the exhaust air is used to heat a separate metal hydride container. In this case, the heat is only partially used instead of being more closely coupled because of the heat transfer resistances in the system. To achieve better heat integration, a novel scheme is proposed whereby hydrogen storage and single fuel cells are more closely coupled. Based on this idea, metal hydride containers in the form of cooling plates were assembled between each pair of cells in the stack so that the heat could be directly transferred to a metal hydride container of much larger surface-to-volume ratio than conventional separate containers. A heat coupled fuel cell portable power source with 10 cells and 11 metal hydride containers was constructed and the experimental results show that this scheme is beneficial for the heat management of fuel cell stack.

  20. Artificial exomuscle investigations for applications--metal hydride.

    Science.gov (United States)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bédard, Stéphane

    2007-03-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software.

  1. Artificial exomuscle investigations for applications-metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bedard, Stephane [Victhom Human Bionics Inc., Saint-Augustin-de-Desmaures, QC (Canada)

    2007-03-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software. (review article)

  2. A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

    Science.gov (United States)

    Zhou, Chengshang

    Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof

  3. Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysis of N-ethylbenzamide or ethyl benzoate.

    Science.gov (United States)

    Yamabe, Shinichi; Guan, Wei; Sakaki, Shigeyoshi

    2013-01-01

    Reaction paths of base-catalyzed hydrolyses of isoelectronic substrates, Ph-C(=O)-X-Et [X = O (ethyl benzoate) and X = NH (N-ethylbenzamide)], were traced by DFT calculations. To simulate bond interchanges accompanied by proton transfers, a cluster model of Ph-C(=O)-X-Et + OH(-)(H(2)O)(16) was employed. For X = O, three elementary processes and for X = NH four ones were obtained. The rate-determining step of X = O is the first TS (TS1, the OH(-) addition step), while that of X = NH is TS2. TS2 of X = NH leads to a novel Mulliken charge-transfer complex, Ph-(OH)(O=)C∙∙∙N(H(2))-Et. The superiority or inferiority between the direct nucleophilic process or the general base-catalyzed process for TS1 was examined with the model Ph-C(=O)-X-Et + OH(-)(H(2)O)(n), n = 3, 5, 8, 12, 16, 24 and 32. The latter process was calculated to be more favorable regardless of the number (n, except n = 3) of water molecules. The counter ion Na(+) works unfavorably on the ester hydrolysis, particularly on TS1. A minimal model of TS1 was proposed and was found to be insensitive to n.

  4. Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysis of N-ethylbenzamide or ethyl benzoate

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2013-01-01

    Full Text Available Reaction paths of base-catalyzed hydrolyses of isoelectronic substrates, Ph–C(=O–X–Et [X = O (ethyl benzoate and X = NH (N-ethylbenzamide], were traced by DFT calculations. To simulate bond interchanges accompanied by proton transfers, a cluster model of Ph–C(=O–X–Et + OH−(H2O16 was employed. For X = O, three elementary processes and for X = NH four ones were obtained. The rate-determining step of X = O is the first TS (TS1, the OH− addition step, while that of X = NH is TS2. TS2 of X = NH leads to a novel Mulliken charge-transfer complex, Ph–(OH(O=C∙∙∙N(H2–Et. The superiority or inferiority between the direct nucleophilic process or the general base-catalyzed process for TS1 was examined with the model Ph–C(=O–X–Et + OH−(H2On, n = 3, 5, 8, 12, 16, 24 and 32. The latter process was calculated to be more favorable regardless of the number (n, except n = 3 of water molecules. The counter ion Na+ works unfavorably on the ester hydrolysis, particularly on TS1. A minimal model of TS1 was proposed and was found to be insensitive to n.

  5. NUMERICAL ANALYSIS FOR HYDRIDING IN METAL HYDRIDE HYDROGEN STORAGE TANK%金属氢化物储氢器吸氢过程的数值分析

    Institute of Scientific and Technical Information of China (English)

    叶建华; 蒋利军; 李志念; 刘晓鹏; 王树茂

    2011-01-01

    Based on the principle of hydride adsorption, a one-dimensional mathematical model for hydriding in a cylindrical metal hydride hydrogen storage tank was established. The heat and mass transfer of metal hydride beds was computed by finite difference method. The variation in temperature and hydrogen concentration at different radial positions of the hydride layer was analyzed during the process of hydriding. The effects of supply pressure, heat convection coefficient and hydride layer radial thickness on the hydriding was studied. It is shown that hydride formation initially takes place uniformly all over the metal hydride layer, but with the process of hydriding, the hydriding rate at the core region is gradually slower than one at surface region. The increase of supply pressure and heat convection coefficient can accelerate the hydriding of the hydrogen storage tank. The effect of hydride layer radial thickness is significant on the hydriding rate, and the thinner hydride layer, the higher the hydriding rate.%基于金属氢化物吸氢基本特性,建立圆柱形金属氢化物储氢器吸氢过程的-维数学物理模型.采用有限差分法对金属氢化物床体的传热传质进行计算.分别研究金属氢化物床体各处温度和氢含量在吸氢过程中的变化以及氢气压力、对流传热系数和金属氢化物床体径向厚度对金属氢化物吸氢过程的影响.计算结果表明:初始阶段金属氢化物床均匀吸氢,但随着氢化过程的进行,其中心区域的吸氢速率逐渐低于边缘区域;增加吸氢压力、提高对流传热系数均可促进储氢器的吸氢;金属氢化物床的径向厚度对吸氢速率影响很大,金属氢化物床越薄,氢化反应的速度越快.

  6. Theoretical study on hydrogenation catalysts containing a metal hydride as additional hydrogen supply

    NARCIS (Netherlands)

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

    1992-01-01

    A hypothetical hydrogenation catalyst consisting of porous, catalytically active particles embedded with metal hydride powder was evaluated. The metal hydride provides temporarily additional hydrogen if the mass transfer rate of the hydrogen to the internal of the particle is not sufficient. A numer

  7. Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins.

    Science.gov (United States)

    Liang, Jiang-Lin; Huang, Jie-Sheng; Yu, Xiao-Qi; Zhu, Nianyong; Che, Chi-Ming

    2002-04-02

    Chiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*)(CO)(EtOH)] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99 % substrate conversions and up to 94 % aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32 % and amide selectivities of up to 91 %. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)(2) + NH(2)SO(2)Me", affording the N-substituted methanesulfonamides in up to 56 % ee with substrate conversions of up to 34 % and amide selectivities of up to 92 %. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)(2) + NH(2)R (R=Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49 % and amide selectivities of up to 90 % (alpha:beta ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)(2)] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2- (4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5x10(-3) dm(3

  8. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

    Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

    2002-01-01

    The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

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

    Science.gov (United States)

    Ni, Shao-Fei; Dang, Li

    2016-02-14

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

  10. Air and metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Lampinen, M.; Noponen, T. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Applied Thermodynamics

    1998-12-31

    The main goal of the air and metal hydride battery project was to enhance the performance and manufacturing technology of both electrodes to such a degree that an air-metal hydride battery could become a commercially and technically competitive power source for electric vehicles. By the end of the project it was possible to demonstrate the very first prototype of the air-metal hydride battery at EV scale, achieving all the required design parameters. (orig.)

  11. Hydrogen Outgassing from Lithium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L N; Schildbach, M A; Smith, R A; Balazs1, B; McLean II, W

    2006-04-20

    Lithium hydride is a nuclear material with a great affinity for moisture. As a result of exposure to water vapor during machining, transportation, storage and assembly, a corrosion layer (oxide and/or hydroxide) always forms on the surface of lithium hydride resulting in the release of hydrogen gas. Thermodynamically, lithium hydride, lithium oxide and lithium hydroxide are all stable. However, lithium hydroxides formed near the lithium hydride substrate (interface hydroxide) and near the sample/vacuum interface (surface hydroxide) are much less thermally stable than their bulk counterpart. In a dry environment, the interface/surface hydroxides slowly degenerate over many years/decades at room temperature into lithium oxide, releasing water vapor and ultimately hydrogen gas through reaction of the water vapor with the lithium hydride substrate. This outgassing can potentially cause metal hydriding and/or compatibility issues elsewhere in the device. In this chapter, the morphology and the chemistry of the corrosion layer grown on lithium hydride (and in some cases, its isotopic cousin, lithium deuteride) as a result of exposure to moisture are investigated. The hydrogen outgassing processes associated with the formation and subsequent degeneration of this corrosion layer are described. Experimental techniques to measure the hydrogen outgassing kinetics from lithium hydride and methods employing the measured kinetics to predict hydrogen outgassing as a function of time and temperature are presented. Finally, practical procedures to mitigate the problem of hydrogen outgassing from lithium hydride are discussed.

  12. Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

    Directory of Open Access Journals (Sweden)

    Márcio José da Silva

    2013-01-01

    Full Text Available A novel process was developed for oxidative desulfurization (ODS in the absence of a phase transfer catalyst (PTC using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by acetonitrile, reducing the sulfur content of isooctane from the 1000 ppm to  H3PMo12O40 > AlPW12O40 > H3PW12O40. The absence of a PTC, acidic organic peroxides, and the use of hydrogen peroxide, an environmentally benign oxidant, make up the positive aspects of AlPMo12O40-catalyzed ODS reactions. In these reactions, high rates of DBT removal (ca. 100% were achieved within a short time (ca. 2 hours and under mild reaction conditions.

  13. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  14. Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

    Science.gov (United States)

    Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

    2011-01-01

    Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

  15. Studies on the mechanism of electron bifurcation catalyzed by electron transferring flavoprotein (Etf) and butyryl-CoA dehydrogenase (Bcd) of Acidaminococcus fermentans.

    Science.gov (United States)

    Chowdhury, Nilanjan Pal; Mowafy, Amr M; Demmer, Julius K; Upadhyay, Vikrant; Koelzer, Sebastian; Jayamani, Elamparithi; Kahnt, Joerg; Hornung, Marco; Demmer, Ulrike; Ermler, Ulrich; Buckel, Wolfgang

    2014-02-21

    Electron bifurcation is a fundamental strategy of energy coupling originally discovered in the Q-cycle of many organisms. Recently a flavin-based electron bifurcation has been detected in anaerobes, first in clostridia and later in acetogens and methanogens. It enables anaerobic bacteria and archaea to reduce the low-potential [4Fe-4S] clusters of ferredoxin, which increases the efficiency of the substrate level and electron transport phosphorylations. Here we characterize the bifurcating electron transferring flavoprotein (EtfAf) and butyryl-CoA dehydrogenase (BcdAf) of Acidaminococcus fermentans, which couple the exergonic reduction of crotonyl-CoA to butyryl-CoA to the endergonic reduction of ferredoxin both with NADH. EtfAf contains one FAD (α-FAD) in subunit α and a second FAD (β-FAD) in subunit β. The distance between the two isoalloxazine rings is 18 Å. The EtfAf-NAD(+) complex structure revealed β-FAD as acceptor of the hydride of NADH. The formed β-FADH(-) is considered as the bifurcating electron donor. As a result of a domain movement, α-FAD is able to approach β-FADH(-) by about 4 Å and to take up one electron yielding a stable anionic semiquinone, α-FAD, which donates this electron further to Dh-FAD of BcdAf after a second domain movement. The remaining non-stabilized neutral semiquinone, β-FADH(•), immediately reduces ferredoxin. Repetition of this process affords a second reduced ferredoxin and Dh-FADH(-) that converts crotonyl-CoA to butyryl-CoA.

  16. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

    2005-12-15

    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  17. Design and Fabricate a Metallic Hydride Heat Pump with a Cooling Capacity of 9000 BTU/H

    Science.gov (United States)

    1989-02-07

    I ERGENICS, INC. N 681 Lawl Ins Road Wyckoff. NJ 07481 DESIGN AND FABRICATE A METALLIC HYDRIDE HEAT PUMP WITH A COOLING CAPACITY OF 9000 BTU/H...air conditioning unit employing a metal hydride heat pump and a silicone heat transfer fluid. The contract was subsequently modified on 29 September 3...for thermally driven ECE systems. Metal hydride heat pumps were proposed as for this application.. However, only laboratory bench experiments have

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

    Institute of Scientific and Technical Information of China (English)

    CETIN,Ahmet; DAYAN,Osman

    2009-01-01

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

  19. Photogeneration of Hydride Donors and Their Use Toward CO2 Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Fujita,E.; Muckerman, J.T.; Polyansky, D.E.

    2009-06-07

    Despite substantial effort, no one has succeeded in efficiently producing methanol from CO2 using homogeneous photocatalytic systems. We are pursuing reaction schemes based on a sequence of hydride-ion transfers to carry out stepwise reduction of CO2 to methanol. We are using hydride-ion transfer from photoproduced C-H bonds in metal complexes with bio-inspired ligands (i.e., NADH-like ligands) that are known to store one proton and two electrons.

  20. Searching for the minimum energy path in the sulfuryl transfer reaction catalyzed by human estrogen sulfotransferase: Role of enzyme dynamics

    Science.gov (United States)

    Lin, Ping; Yang, Weitao; Pedersen, Lars C.; Negishi, Masa; Pedersen, Lee G.

    The enzymatic transfer of a sulfuryl group from the ubiquitous biological source of sulfate 3?-phosphoadenosine 5?-phosphosulfate (PAPS) to estrogen is investigated by the pseudo-bond quantum mechanical/molecular mechanical method (QM/MM) method. Calculations of the reaction path are performed starting with models based on two crystal structures, which differ in information about the cofactor and substrates. In addition, a subsequent relaxation of the enzyme was performed with the found transition state frozen, followed by redetermination of the path. An activation barrier of 22 kcal/mol is estimated. The reaction mechanism features a proton transfer from the estrogen to a catalytic histidine followed by the rate determining SO3 transfer. The mechanism found is largely dissociative.

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

    Science.gov (United States)

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

    2015-03-01

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

  2. Ab-initio study of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Ramesh [Dept. of Physics, Feroze Gandhi Insititute of Engineering and Technology, Raebareli-229001 (India); Shukla, Seema, E-mail: sharma.yamini62@gmail.com; Dwivedi, Shalini, E-mail: sharma.yamini62@gmail.com; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Theoretical Condensed Matter Physics Laboratory, Dept. of Physics Feroze Gandhi College, Raebareli-229001 (India)

    2014-04-24

    We have performed ab initio self consistent calculations based on Full potential linearized augmented plane wave (FP-LAPW) method to investigate the optical and thermal properties of yttrium hydrides. From the band structure and density of states, the optical absorption spectra and specific heats have been calculated. The band structure of Yttrium metal changes dramatically due to hybridization of Y sp orbitals with H s orbitals and there is a net charge transfer from metal to hydrogen site. The electrical resistivity and specific heats of yttrium hydrides are lowered but the thermal conductivity is slightly enhanced due to increase in scattering from hydrogen sites.

  3. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir

    2015-11-28

    This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

  4. A novel mechanism of sulfur transfer catalyzed by O-acetylhomoserine sulfhydrylase in the methionine-biosynthetic pathway of Wolinella succinogenes

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Timothy H. [Cornell University, Ithaca, New York 14853-1301 (United States); Krishnamoorthy, Kalyanaraman; Begley, Tadhg P., E-mail: begley@tamu.edu [Texas A& M University, College Station, TX 77842 (United States); Ealick, Steven E., E-mail: begley@tamu.edu [Cornell University, Ithaca, New York 14853-1301 (United States)

    2011-10-01

    MetY is the first reported structure of an O-acetylhomoserine sulfhydrylase that utilizes a protein thiocarboxylate intermediate as the sulfur source in a novel methionine-biosynthetic pathway instead of catalyzing a direct sulfhydrylation reaction. O-Acetylhomoserine sulfhydrylase (OAHS) is a pyridoxal 5′-phosphate (PLP) dependent sulfide-utilizing enzyme in the l-cysteine and l-methionine biosynthetic pathways of various enteric bacteria and fungi. OAHS catalyzes the conversion of O-acetylhomoserine to homocysteine using sulfide in a process known as direct sulfhydrylation. However, the source of the sulfur has not been identified and no structures of OAHS have been reported in the literature. Here, the crystal structure of Wolinella succinogenes OAHS (MetY) determined at 2.2 Å resolution is reported. MetY crystallized in space group C2 with two monomers in the asymmetric unit. Size-exclusion chromatography, dynamic light scattering and crystal packing indicate that the biological unit is a tetramer in solution. This is further supported by the crystal structure, in which a tetramer is formed using a combination of noncrystallographic and crystallographic twofold axes. A search for structurally homologous proteins revealed that MetY has the same fold as cystathionine γ-lyase and methionine γ-lyase. The active sites of these enzymes, which are also PLP-dependent, share a high degree of structural similarity, suggesting that MetY belongs to the γ-elimination subclass of the Cys/Met metabolism PLP-dependent family of enzymes. The structure of MetY, together with biochemical data, provides insight into the mechanism of sulfur transfer to a small molecule via a protein thiocarboxylate intermediate.

  5. A highly sensitive fluorescence resonance energy transfer aptasensor for staphylococcal enterotoxin B detection based on exonuclease-catalyzed target recycling strategy

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Shijia; Duan, Nuo; Ma, Xiaoyuan; Xia, Yu; Wang, Hongxin; Wang, Zhouping, E-mail: wangzp@jiangnan.edu.cn

    2013-06-11

    Graphical abstract: -- Highlights: •An ultrasensitive FRET aptasensor was developed for staphylococcal enterotoxin B determination. •SEB was recognized by SEB aptamer with high affinity and specificity. •The Mn{sup 2+} doped NaYF{sub 4}:Yb/Er UCNPs used as donor to quencher dye (BHQ{sub 3}) in new FRET. •The fluorescence intensity was prominently amplified using an exonuclease-catalyzed target recycling strategy. -- Abstract: An ultrasensitive fluorescence resonance energy transfer (FRET) bioassay was developed to detect staphylococcal enterotoxin B (SEB), a low molecular exotoxin, using an aptamer-affinity method coupled with upconversion nanoparticles (UCNPs)-sensing, and the fluorescence intensity was prominently enhanced using an exonuclease-catalyzed target recycling strategy. To construct this aptasensor, both fluorescence donor probes (complementary DNA{sub 1}–UCNPs) and fluorescence quencher probes (complementary DNA{sub 2}–Black Hole Quencher{sub 3} (BHQ{sub 3})) were hybridized to an SEB aptamer, and double-strand oligonucleotides were fabricated, which quenched the fluorescence of the UCNPs via FRET. The formation of an aptamer–SEB complex in the presence of the SEB analyte resulted in not only the dissociation of aptamer from the double-strand DNA but also both the disruption of the FRET system and the restoration of the UCNPs fluorescence. In addition, the SEB was liberated from the aptamer–SEB complex using exonuclease I, an exonuclease specific to single-stranded DNA, for analyte recycling by selectively digesting a particular DNA (SEB aptamer). Based on this exonuclease-catalyzed target recycling strategy, an amplified fluorescence intensity could be produced using different SEB concentrations. Using optimized experimental conditions produced an ultrasensitive aptasensor for the detection of SEB, with a wide linear range of 0.001–1 ng mL{sup −1} and a lower detection limit (LOD) of 0.3 pg mL{sup −1} SEB (at 3σ). The fabricated

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  7. Metal Hydride Compression

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Bowman, Robert [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Smith, Barton [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Anovitz, Lawrence [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jensen, Craig [Hawaii Hydrogen Carriers LLC, Honolulu, HI (United States)

    2017-07-01

    Conventional hydrogen compressors often contribute over half of the cost of hydrogen stations, have poor reliability, and have insufficient flow rates for a mature FCEV market. Fatigue associated with their moving parts including cracking of diaphragms and failure of seal leads to failure in conventional compressors, which is exacerbated by the repeated starts and stops expected at fueling stations. Furthermore, the conventional lubrication of these compressors with oil is generally unacceptable at fueling stations due to potential fuel contamination. Metal hydride (MH) technology offers a very good alternative to both conventional (mechanical) and newly developed (electrochemical, ionic liquid pistons) methods of hydrogen compression. Advantages of MH compression include simplicity in design and operation, absence of moving parts, compactness, safety and reliability, and the possibility to utilize waste industrial heat to power the compressor. Beyond conventional H2 supplies of pipelines or tanker trucks, another attractive scenario is the on-site generating, pressuring and delivering pure H2 at pressure (≥ 875 bar) for refueling vehicles at electrolysis, wind, or solar generating production facilities in distributed locations that are too remote or widely distributed for cost effective bulk transport. MH hydrogen compression utilizes a reversible heat-driven interaction of a hydride-forming metal alloy with hydrogen gas to form the MH phase and is a promising process for hydrogen energy applications [1,2]. To deliver hydrogen continuously, each stage of the compressor must consist of multiple MH beds with synchronized hydrogenation & dehydrogenation cycles. Multistage pressurization allows achievement of greater compression ratios using reduced temperature swings compared to single stage compressors. The objectives of this project are to investigate and demonstrate on a laboratory scale a two-stage MH hydrogen (H2) gas compressor with a

  8. Exploring "aerogen-hydride" interactions between ZOF2 (Z = Kr, Xe) and metal hydrides: An ab initio study

    Science.gov (United States)

    Esrafili, Mehdi D.; Mohammadian-Sabet, Fariba

    2016-06-01

    In this work, a new σ-hole interaction formed between ZOF2 (Z = Kr and Xe) as the Lewis acid and a series of metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CN, CH3) is reported. The nature of this interaction, called "aerogen-hydride" interaction, is unveiled by molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. Our results indicate that the aerogen-hydride interactions are quite strong and can be comparable in strength to other σ-hole bonds. An important charge-transfer interaction is also associated with the formation of OF2Z⋯HMX complexes.

  9. Functional-Group-Tolerant, Silver-Catalyzed N-N Bond Formation by Nitrene Transfer to Amines.

    Science.gov (United States)

    Maestre, Lourdes; Dorel, Ruth; Pablo, Óscar; Escofet, Imma; Sameera, W M C; Álvarez, Eleuterio; Maseras, Feliu; Díaz-Requejo, M Mar; Echavarren, Antonio M; Pérez, Pedro J

    2017-02-15

    Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI═NTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N-N bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.

  10. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  11. Hydride development for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.; Yang, N.Y.C. [Sandia National Lab., Livermore, CA (United States); Sandrock, G. [SunaTech, Inc., Ringwood, NJ (United States)

    1996-10-01

    The purpose of this project is to develop and demonstrate improved hydride materials for hydrogen storage. The work currently is organized into four tasks: hydride development, bed fabrication, materials support for engineering systems, and IEA Annex 12 activities. At the present time, hydride development is focused on Mg alloys. These materials generally have higher weight densities for storing hydrogen than rare earth or transition metal alloys, but suffer from high operating temperatures, slow kinetic behavior and material stability. The authors approach is to study bulk alloy additions which increase equilibrium overpressure, in combination with stable surface alloy modification and particle size control to improve kinetic properties. This work attempts to build on the considerable previous research in this area, but examines specific alloy systems in greater detail, with attention to known phase properties and structures. The authors have found that specific phases can be produced which have significantly improved hydride properties compared to previous studies.

  12. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    hydrogen. Further evaluation and development of this concept will be performed as follow-on work under another project. However, since the cost of reducing magnesium from magnesium oxide makes up 85% of the cost of the slurry, if hydrogen can be stored many times in the slurry, then the cost of storing hydrogen can be spread over many units of hydrogen and can be significantly reduced from the costs of a chemical hydride system. This may be the most important finding of this project. If the slurry is used to carry a rechargeable hydride, the slurry can be stored in a conventional liquid fuel tank and delivered to a release system as hydrogen is needed. The release system will contain only the hydride needed to produce the hydrogen desired. This is in contrast to conventional designs proposed for other rechargeable hydride systems that store all the hydride in a large and heavy pressure and heat transfer vessel.

  13. Metal hydride air conditioner

    Institute of Scientific and Technical Information of China (English)

    YANG; Ke; DU; Ping; LU; Man-qi

    2005-01-01

    The relationship among the hydrogen storage properties, cycling characteristics and thermal parameters of the metal hydride air conditioning systems was investigated. Based on a new alloy selection model, three pairs of hydrogen storage alloys, LaNi4.4 Mn0.26 Al0.34 / La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1, LaNi4.61Mn0. 26 Al0.13/La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1 and LaNi4.61 Mn0.26 Al0.13/La0.6 Y0.4 Ni4.8 Mn0. 2, were selected as the working materials for the metal hydride air conditioning system. Studies on the factors affecting the COP of the system showed that higher COP and available hydrogen content need the proper operating temperature and cycling time,large hydrogen storage capacity, flat plateau and small hysterisis of hydrogen alloys, proper original input hydrogen content and mass ratio of the pair of alloys. It also needs small conditioning system was established by using LaNi4.61 Mn0.26 Al0. 13/La0.6 Y0.4 Ni4.8 Mn0.2 alloys as the working materials, which showed that under the operating temperature of 180℃/40℃, a low temperature of 13℃ was reached, with COP =0.38 and Wnet =0.09 kW/kg.

  14. Geoneutrino and Hydridic Earth model

    CERN Document Server

    Bezrukov, Leonid

    2013-01-01

    Uranium, Thorium and Potassium-40 abundances in the Earth were calculated in the frame of Hydridic Earth model. Terrestrial heat producton from U, Th and K40 decays was calculated also. We must admit the existance of Earth expansion process to understand the obtained large value of terrestrial heat producton. The geoneutrino detector with volume more than 5 kT (LENA type) must be constructed to definitely separate between Bulk Silicat Earth model and Hydridic Earth model.

  15. Versatile In Situ Generated N-Boc-Imines: Application to Phase-Transfer-Catalyzed Asymmetric Mannich-Type Reactions.

    Science.gov (United States)

    Kano, Taichi; Kobayashi, Ryohei; Maruoka, Keiji

    2015-07-13

    The efficient construction of nitrogen-containing organic compounds is a major challenge in chemical synthesis. Imines are one of the most important classes of electrophiles for this transformation. However, both the available imines and applicable nucleophiles for them are quite limited given the existing preparative methods. Described herein are imine precursors which generate reactive imines with a wide variety of substituents under mild basic conditions. This approach enables the construction of various nitrogen-containing molecules which cannot be accessed by the traditional approach. The utility of the novel imine precursor was demonstrated in the asymmetric Mannich-type reaction under phase-transfer conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Xylose isomerase in substrate and inhibitor michaelis states: atomic resolution studies of a metal-mediated hydride shift.

    Science.gov (United States)

    Fenn, Timothy D; Ringe, Dagmar; Petsko, Gregory A

    2004-06-01

    Xylose isomerase (E.C. 5.3.1.5) catalyzes the interconversion of aldose and ketose sugars and has an absolute requirement for two divalent cations at its active site to drive the hydride transfer rates of sugar isomerization. Evidence suggests some degree of metal movement at the second metal site, although how this movement may affect catalysis is unknown. The 0.95 A resolution structure of the xylitol-inhibited enzyme presented here suggests three alternative positions for the second metal ion, only one of which appears positioned in a catalytically competent manner. To complete the reaction, an active site hydroxyl species appears appropriately positioned for hydrogen transfer, as evidenced by precise bonding distances. Conversely, the 0.98 A resolution structure of the enzyme with glucose bound in the alpha-pyranose state only shows one of the metal ion conformations at the second metal ion binding site, suggesting that the linear form of the sugar is required to promote the second and third metal ion conformations. The two structures suggest a strong degree of conformational flexibility at the active site, which seems required for catalysis and may explain the poor rate of turnover for this enzyme. Further, the pyranose structure implies that His53 may act as the initial acid responsible for ring opening of the sugar to the aldose form, an observation that has been difficult to establish in previous studies. The glucose ring also appears to display significant segmented disorder in a manner suggestive of ring opening, perhaps lending insight into means of enzyme destabilization of the ground state to promote catalysis. On the basis of these results, we propose a modified version of the bridged bimetallic mechanism for hydride transfer in the case of Streptomyces olivochromogenes xylose isomerase.

  17. Release of hydrogen from nanoconfined hydrides by application of microwaves

    Science.gov (United States)

    Sanz-Moral, Luis Miguel; Navarrete, Alexander; Sturm, Guido; Link, Guido; Rueda, Miriam; Stefanidis, Georgios; Martín, Ángel

    2017-06-01

    The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m2/g and 1.41 cm3/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.

  18. Optimization of Internal Cooling Fins for Metal Hydride Reactors

    Directory of Open Access Journals (Sweden)

    Vamsi Krishna Kukkapalli

    2016-06-01

    Full Text Available Metal hydride alloys are considered as a promising alternative to conventional hydrogen storage cylinders and mechanical hydrogen compressors. Compared to storing in a classic gas tank, metal hydride alloys can store hydrogen at nearly room pressure and use less volume to store the same amount of hydrogen. However, this hydrogen storage method necessitates an effective way to reject the heat released from the exothermic hydriding reaction. In this paper, a finned conductive insert is adopted to improve the heat transfer in the cylindrical reactor. The fins collect the heat that is volumetrically generated in LaNi5 metal hydride alloys and deliver it to the channel located in the center, through which a refrigerant flows. A multiple-physics modeling is performed to analyze the transient heat and mass transfer during the hydrogen absorption process. Fin design is made to identify the optimum shape of the finned insert for the best heat rejection. For the shape optimization, use of a predefined transient heat generation function is proposed. Simulations show that there exists an optimal length for the fin geometry.

  19. Physics of hydride fueled PWR

    Science.gov (United States)

    Ganda, Francesco

    The first part of the work presents the neutronic results of a detailed and comprehensive study of the feasibility of using hydride fuel in pressurized water reactors (PWR). The primary hydride fuel examined is U-ZrH1.6 having 45w/o uranium: two acceptable design approaches were identified: (1) use of erbium as a burnable poison; (2) replacement of a fraction of the ZrH1.6 by thorium hydride along with addition of some IFBA. The replacement of 25 v/o of ZrH 1.6 by ThH2 along with use of IFBA was identified as the preferred design approach as it gives a slight cycle length gain whereas use of erbium burnable poison results in a cycle length penalty. The feasibility of a single recycling plutonium in PWR in the form of U-PuH2-ZrH1.6 has also been assessed. This fuel was found superior to MOX in terms of the TRU fractional transmutation---53% for U-PuH2-ZrH1.6 versus 29% for MOX---and proliferation resistance. A thorough investigation of physics characteristics of hydride fuels has been performed to understand the reasons of the trends in the reactivity coefficients. The second part of this work assessed the feasibility of multi-recycling plutonium in PWR using hydride fuel. It was found that the fertile-free hydride fuel PuH2-ZrH1.6, enables multi-recycling of Pu in PWR an unlimited number of times. This unique feature of hydride fuels is due to the incorporation of a significant fraction of the hydrogen moderator in the fuel, thereby mitigating the effect of spectrum hardening due to coolant voiding accidents. An equivalent oxide fuel PuO2-ZrO2 was investigated as well and found to enable up to 10 recycles. The feasibility of recycling Pu and all the TRU using hydride fuels were investigated as well. It was found that hydride fuels allow recycling of Pu+Np at least 6 times. If it was desired to recycle all the TRU in PWR using hydrides, the number of possible recycles is limited to 3; the limit is imposed by positive large void reactivity feedback.

  20. Mechanistic Insight into the Intramolecular Benzylic C-H Nitrene Insertion Catalyzed by Bimetallic Paddlewheel Complexes: Influence of the Metal Centers.

    Science.gov (United States)

    Zhang, Xuepeng; Xu, Huiying; Liu, Xueping; Phillips, David Lee; Zhao, Cunyuan

    2016-05-17

    The intramolecular benzylic C-H amination catalyzed by bimetallic paddlewheel complexes was investigated by using density functional theory calculations. The metal-metal bonding characters were investigated and the structures featuring either a small HOMO-LUMO gap or a compact SOMO energy scope were estimated to facilitate an easier one-electron oxidation of the bimetallic center. The hydrogen-abstraction step was found to occur through three manners, that is, hydride transfer, hydrogen migration, and proton transfer. The imido N species are more preferred in the Ru-Ru and Pd-Mn cases whereas coexisting N species, namely, singlet/triplet nitrene and imido, were observed in the Rh-Rh and Pd-Co cases. On the other hand, the triplet nitrene N species were found to be predominant in the Pd-Ni and Pd-Zn systems. A concerted asynchronous mechanism was found to be modestly favorable in the Rh-Rh-catalyzed reactions whereas the Pd-Co-catalyzed reactions demonstrated a slight preference for a stepwise pathway. Favored stepwise pathways were seen in each Ru-Ru- and Pd-Mn-catalyzed reactions and in the triplet nitrene involved Pd-Ni and Pd-Zn reactions. The calculations suggest the feasibility of the Pd-Mn, Pd-Co, and Pd-Ni paddlewheel complexes as being economical alternatives for the expensive dirhodium/diruthenium complexes in C-H amination catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A New Reducing Regent: Dichloroindium Hydride

    Institute of Scientific and Technical Information of China (English)

    A. BABA; I. SHIBATA; N. HAYASHI

    2005-01-01

    @@ 1Introduction Among the hydride derivatives of group 13 elements, various types of aluminum hydrides and boron hydrides have been employed as powerful reduction tools. Indium hydrides have not received much attention,whereas the synthesis of indium trihydride (InH3) was reported several decades ago[1]. There have been no precedents for monometallic indium hydrides having practical reactivity, while activated hydrides such as an ate complex LiPhn InH4-n (n = 0- 2) and phosphine-coordinated indium hydrides readily reduce carbonyl compounds. In view of this background, we focused on the development of dichloroindium hydrides (Cl2InH) as novel reducing agents that bear characteristic features in both ionic and radical reactions.

  2. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

    This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

  3. Complex and liquid hydrides for energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Callini, Elsa; Atakli, Zuleyha Özlem Kocabas; Hauback, Bjørn C.; Orimo, Shin-ichi; Jensen, Craig; Dornheim, Martin; Grant, David; Cho, Young Whan; Chen, Ping; Hjörvarsson, Bjørgvin; de Jongh, Petra; Weidenthaler, Claudia; Baricco, Marcello; Paskevicius, Mark; Jensen, Torben R.; Bowden, Mark E.; Autrey, Thomas S.; Züttel, Andreas

    2016-03-10

    The research on complex hydrides for hydrogen storage was imitated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized and the knowledge on the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant part of the research groups active in the field of complex hydrides are collaborators in the IEA task 32. This paper reports about the important issues in the field of the complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides and their thermodynamic properties, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and excellent summary of the recent achievements.

  4. Luminescent properties of aluminum hydride

    Energy Technology Data Exchange (ETDEWEB)

    Baraban, A.P.; Gabis, I.E.; Dmitriev, V.A. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Dobrotvorskii, M.A., E-mail: mstislavd@gmail.com [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Kuznetsov, V.G. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Matveeva, O.P. [National Mineral Resources University, Saint Petersburg 199106 (Russian Federation); Titov, S.A. [Petersburg State University of Railway Transport, Saint-Petersburg 190031 (Russian Federation); Voyt, A.P.; Elets, D.I. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation)

    2015-10-15

    We studied cathodoluminescence and photoluminescence of α-AlH{sub 3}– a likely candidate for use as possible hydrogen carrier in hydrogen-fueled vehicles. Luminescence properties of original α-AlH{sub 3} and α-AlH{sub 3} irradiated with ultraviolet were compared. The latter procedure leads to activation of thermal decomposition of α-AlH{sub 3} and thus has a practical implementation. We showed that the original and UV-modified aluminum hydride contain luminescence centers ‐ structural defects of the same type, presumably hydrogen vacancies, characterized by a single set of characteristic bands of radiation. The observed luminescence is the result of radiative intracenter relaxation of the luminescence center (hydrogen vacancy) excited by electrons or photons, and its intensity is defined by the concentration of vacancies, and the area of their possible excitation. UV-activation of the dehydrogenation process of aluminum hydride leads to changes in the spatial distribution of the luminescence centers. For short times of exposure their concentration increases mainly in the surface regions of the crystals. At high exposures, this process extends to the bulk of the aluminum hydride and ends with a decrease in concentration of luminescence centers in the surface region. - Highlights: • Aluminum hydride contains hydrogen vacancies which serve as luminescence centers. • The luminescence is the result of radiative relaxation of excited centers. • Hydride UV-irradiation alters distribution and concentration of luminescence centers.

  5. Design, Synthesis, and Validation of an Effective, Reusable Silicon-Based Transfer Agent for Room-Temperature Pd-Catalyzed Cross-Coupling Reactions of Aryl and Heteroaryl Chlorides with Readily Available Aryl Lithium Reagents.

    Science.gov (United States)

    Martinez-Solorio, Dionicio; Melillo, Bruno; Sanchez, Luis; Liang, Yong; Lam, Erwin; Houk, K N; Smith, Amos B

    2016-02-17

    A reusable silicon-based transfer agent (1) has been designed, synthesized, and validated for effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent (1) is easily prepared via a one-step protocol. Importantly, this "green" CCR protocol circumvents prefunctionalization, isolation of organometallic cross-coupling partners, and/or stoichiometric waste aside from LiCl. DFT calculations support a σ-bond metathesis mechanism during transmetalation and lead to insights on the importance of the CF3 groups.

  6. Method of producing a chemical hydride

    Science.gov (United States)

    Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

    2007-11-13

    A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

  7. Hydrogen, lithium, and lithium hydride production

    Science.gov (United States)

    Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

    2014-03-25

    A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

  8. 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 (hydrogen production 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.

  9. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today......’s hydride batteries, but a much poorer stability towards repeated charge/discharge cycling. The aim was to see if the cycleability of CaNi5 could be enhanced enough by modifications to make the compound a suitable electrode material. An alloying method based on mechanical alloying in a planetary ball mill...... by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated...

  10. [Investigation of enhancing effect for hydride generation-atomic fluorescence of transition metal elements].

    Science.gov (United States)

    Sun, Han-Wen; Suo, Ran

    2008-11-01

    A mechanism of hydride generation based on disassembly reaction of hydrogen-transferred interim state [M(BH4)m]* was developed by investigating the effect of reaction medium acidity on hydride generation. The effects of Co2+ and Ni2+, phenanthroline and 8-hydroxyquinoline on hydride generation-atomic fluorescence signals of Zn, Cd, Cu and Ni were studied, respectively, and their enhancing mechnism was discussed. The enhancing effect Co2+ and Ni2+ on the fluorescence signals of Zn and Cd was due to the increase in transmission efficiency of hydride of Zn and Cd. There was a synergic enhancing effect between phenanthroline or 8-hydroxyquinoline and Co2+ on the fluorescence signals of Zn and Cd, however no synergic enhancing effect between phenanthroline and 8-hydroxyquinoline on the fluorescence signals of Zn and Cd. The simulative action of cationic surfactant, anion surfactant and non-ionic surfactant surfactant to hydride generation was investigated. It is shown that both cationic surfactant and non-ionic surfactant have obvious enhancing effect on the fluorescence signals of analytes because of the decrease in surface tension of reaction solution. The release characteristics of hydride from the absorption solution containing surfactant was ulteriorly examined by using graphite furnace atomic absorption spectrometry, and the mechanism of enhancing effect of surfactant on hydride generation and transmission was proposed.

  11. Development of a component design tool for metal hydride heat pumps

    Science.gov (United States)

    Waters, Essene L.

    Given current demands for more efficient and environmentally friendly energy sources, hydrogen based energy systems are an increasingly popular field of interest. Within the field, metal hydrides have become a prominent focus of research due to their large hydrogen storage capacity and relative system simplicity and safety. Metal hydride heat pumps constitute one such application, in which heat and hydrogen are transferred to and from metal hydrides. While a significant amount of work has been done to study such systems, the scope of materials selection has been quite limited. Typical studies compare only a few metal hydride materials and provide limited justification for the choice of those few. In this work, a metal hydride component design tool has been developed to enable the targeted down-selection of an extensive database of metal hydrides to identify the most promising materials for use in metal hydride thermal systems. The material database contains over 300 metal hydrides with various physical and thermodynamic properties included for each material. Sub-models for equilibrium pressure, thermophysical data, and default properties are used to predict the behavior of each material within the given system. For a given thermal system, this tool can be used to identify optimal materials out of over 100,000 possible hydride combinations. The selection tool described herein has been applied to a stationary combined heat and power system containing a high-temperature proton exchange membrane (PEM) fuel cell, a hot water tank, and two metal hydride beds used as a heat pump. A variety of factors can be used to select materials including efficiency, maximum and minimum system pressures, pressure difference, coefficient of performance (COP), and COP sensitivity. The targeted down-selection of metal hydrides for this system focuses on the system's COP for each potential pair. The values of COP and COP sensitivity have been used to identify pairs of highest interest for

  12. Hydrogen Storage in Metal Hydrides

    Science.gov (United States)

    1990-08-01

    Hydrogen Storage Capacity Hydride by weight (%) [1) by volume (g/ml) [2] MgH2 7.00 0.101 Mg2NiH4 3.84 0,081 Mg2CuH4 2.04 - - 27 ...Include Security Classification) Hydrogen Storage in Metal Hydrides (U) 12. PERSONAL AUTHOR(S) DelaRosa, Mark J. 13a. TYPE OF REPORT 13b. TIME...objective of this program was to develop an economical process for pr-ducing a lightweight hydrogen storage medium by the chemical vapor infiltration

  13. Crystallography of shear transformations in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Cassidy, Michael Philip [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1978-01-01

    The crystallography and substructure of the transformations which have been hypothesized as involving a martensitic shear, and which occur between zirconium hydrides were investigated. Specifically, the formation of gamma zirconium hydride from delta hydride and the delta hydride to epsilon hydride transformation were studied. The habit planes, orientation relationships, lattice invariant shears, and interface structures were determined by transmission electron microscopy and diffraction. Surface tilts were observed and measured with an interference microscope. The direction and magnitude of the shape strain produced by the formation of gamma were determined by the measurement of fiducial scratch displacements. These results were compared with the phenomenological crystallographic theory of martensitic transformations.

  14. Characteristics and Applications of Metal Hydrides

    Science.gov (United States)

    Egan, G. J.; Lynch, F. E.

    1987-01-01

    Report discusses engineering principles of uses of metal hydrides in spacecraft. Metal hydrides absorb, store, pump, compress, and expand hydrogen gas. Additionally, they release or absorb sizeable amounts of heat as they form and decompose - property adapted for thermal-energy management or for propulsion. Describes efforts to: Identify heat sources and sinks suitable for driving metal hydride thermal cycles in spacecraft; develop concepts for hydride subsystems employing available heating and cooling methods; and produce data base on estimated sizes, masses, and performances of hydride devices for spacecraft.

  15. ReBr(CO)5-Catalyzed Knoevenagel Condensation

    Institute of Scientific and Technical Information of China (English)

    ZUO Wei-xiong; HUA Rui-mao; SUN Hong-bin

    2004-01-01

    Knoevenagel condensations are especially important reactions for the synthesis of alkene compounds having electron-withdrawing groups such as COR,CN,COOR,NO2 etc. Recently,transition metal hydride ruthenium1, hydride and polyhydride rhenium2, and polyhydride iridium complexes have been found to be the efficient catalysts for Knoevenagle condensation. However the mentioned-above transition metal hydride complexes are not easily prepared. In addition, all of them are oxygen and H2O-sensitive, unstable compands. Therefor the catalytic reactions are required to be carried out under an inert atmosphere, and using the prepurified reagent.In the paper, We wish to report the development of Knoevenagel condensation catalyzed by ReBr(CO)5 under an air atmosphere in the absence of solvent.All the experiments were carried out under 1atm, without solvent.The resuIts of the representative Knoevenagel condensations are summarized in Table 1.The Knoevenagel reaction with diethyl malonate can be catalyzed by ReBr(CO)5, while the present Knoevenagel reactions catalyzed by transition metal have at least one cyano group in active methylene compouds.A propose mechanism for present catalytic coupling dehydration reactions is also illustrated in the paper.Briefly, this paper reports the ReBr(CO)5-catalyzed Knoevenagel reaction. The reaction is a new method for the Konevenagel condensation.

  16. Characterization of hydrides and delayed hydride cracking in zirconium alloys

    Science.gov (United States)

    Fang, Qiang

    This thesis tries to fill some of the missing gaps in the study of zirconium hydrides with state-of-art experiments, cutting edge tomographical technique, and a novel numerical algorithm. A new hydriding procedure is proposed. The new anode material and solution combination overcomes many drawbacks of the AECLRTM hydriding method and leads to superior hydriding result compared to the AECL RTM hydriding procedure. The DHC crack growth velocity of as-received Excel alloy and Zr-2.5Nb alloy together with several different heat treated Excel alloy samples are measured. While it already known that the DHC crack growth velocity increases with the increase of base metal strength, the finding that the transverse plane is the weaker plane for fatigue crack growth despite having higher resistance to DHC crack growth was unexpected. The morphologies of hydrides in a coarse grained Zircally-2 sample have been studied using synchrotron x-rays at ESRF with a new technique called Diffraction Contrast Tomography that uses simultaneous collection of tomographic data and diffraction data to determine the crystallographic orientation of crystallites (grains) in 3D. It has been previously limited to light metals such as Al or Mg (due to the use of low energy x-rays). Here we show the first DCT measurements using high energy x-rays (60 keV), allowing measurements in zirconium. A new algorithm of a computationally effcient way to characterize distributions of hydrides - in particular their orientation and/or connectivity - has been proposed. It is a modification of the standard Hough transform, which is an extension of the Hough transform widely used in the line detection of EBSD patterns. Finally, a basic model of hydrogen migration is built using ABAQUS RTM, which is a mature finite element package with tested modeling modules of a variety of physical laws. The coupling of hydrogen diffusion, lattice expansion, matrix deformation and phase transformation is investigated under

  17. Properties of nanoscale metal hydrides.

    Science.gov (United States)

    Fichtner, Maximilian

    2009-05-20

    Nanoscale hydride particles may exhibit chemical stabilities which differ from those of a macroscopic system. The stabilities are mainly influenced by a surface energy term which contains size-dependent values of the surface tension, the molar volume and an additional term which takes into account a potential reduction of the excess surface energy. Thus, the equilibrium of a nanoparticular hydride system may be shifted to the hydrogenated or to the dehydrogenated side, depending on the size and on the prefix of the surface energy term of the hydrogenated and dehydrogenated material. Additional complexity appears when solid-state reactions of complex hydrides are considered and phase segregation has to be taken into account. In such a case the reversibility of complex hydrides may be reduced if the nanoparticles are free standing on a surface. However, it may be enhanced if the system is enclosed by a nanoscale void which prevents the reaction partners on the dehydrogenated side from diffusing away from each other. Moreover, the generally enhanced diffusivity in nanocrystalline systems may lower the kinetic barriers for the material's transformation and, thus, facilitate hydrogen absorption and desorption.

  18. Role of Pyridine as a Biomimetic Organo-Hydride for Homogeneous Reduction of CO2 to Methanol

    CERN Document Server

    Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

    2014-01-01

    We use quantum chemical calculations to elucidate a viable homogeneous mechanism for pyridine-catalyzed reduction of CO2 to methanol. In the first component of the catalytic cycle, pyridine (Py) undergoes a H+ transfer (PT) to form pyridinium (PyH+) followed by an e- transfer (ET) to produce pyridinium radical (PyH0). Examples of systems to effect this ET to populate the LUMO of PyH+(E0calc ~ -1.3V vs. SCE) to form the solution phase PyH0 via highly reducing electrons include the photo-electrochemical p-GaP system (ECBM ~ -1.5V vs. SCE at pH= 5) and the photochemical [Ru(phen)3]2+/ascorbate system. We predict that PyH0 undergoes further PT-ET steps to form the key closed-shell, dearomatized 1,2-dihydropyridine (PyH2) species. Our proposed sequential PT-ET-PT-ET mechanism transforming Py into PyH2 is consistent with the mechanism described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics the ...

  19. The renaissance of hydrides as energy materials

    Science.gov (United States)

    Mohtadi, Rana; Orimo, Shin-Ichi

    2017-02-01

    Materials based on hydrides have been the linchpin in the development of several practical energy storage technologies, of which the most prominent example is nickel-metal hydride batteries. Motivated by the need to meet the future's energy demand, the past decade has witnessed substantial advancements in the research and development of hydrides as media for hydrogen energy storage. More recently, new and rapidly evolving discoveries have positioned hydrides as highly promising materials for future electrochemical energy storage, such as electrolytes for mono- and divalent batteries, and anodes for lithium-ion batteries. In addition, the potential of hydrides in efficient power transmission has been recently revealed. In this Review, we highlight key advances and illustrate how the versatility of hydrides has not only yielded a meaningful past, but also ensures a very bright future.

  20. Rechargeable metal hydrides for spacecraft application

    Science.gov (United States)

    Perry, J. L.

    1988-01-01

    Storing hydrogen on board the Space Station presents both safety and logistics problems. Conventional storage using pressurized bottles requires large masses, pressures, and volumes to handle the hydrogen to be used in experiments in the U.S. Laboratory Module and residual hydrogen generated by the ECLSS. Rechargeable metal hydrides may be competitive with conventional storage techniques. The basic theory of hydride behavior is presented and the engineering properties of LaNi5 are discussed to gain a clear understanding of the potential of metal hydrides for handling spacecraft hydrogen resources. Applications to Space Station and the safety of metal hydrides are presented and compared to conventional hydride storage. This comparison indicates that metal hydrides may be safer and require lower pressures, less volume, and less mass to store an equivalent mass of hydrogen.

  1. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  2. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  3. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

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

  4. Use of reversible hydrides for hydrogen storage

    Science.gov (United States)

    Darriet, B.; Pezat, M.; Hagenmuller, P.

    1980-01-01

    The addition of metals or alloys whose hydrides have a high dissociation pressure allows a considerable increase in the hydrogenation rate of magnesium. The influence of temperature and hydrogen pressure on the reaction rate were studied. Results concerning the hydriding of magnesium rich alloys such as Mg2Ca, La2Mg17 and CeMg12 are presented. The hydriding mechanism of La2Mg17 and CeMg12 alloys is given.

  5. Inhibited solid propellant composition containing beryllium hydride

    Science.gov (United States)

    Thompson, W. W. (Inventor)

    1978-01-01

    An object of this invention is to provide a composition of beryllium hydride and carboxy-terminated polybutadiene which is stable. Another object of this invention is to provide a method for inhibiting the reactivity of beryllium hydride toward carboxy-terminated polybutadiene. It was found that a small amount of lecithin inhibits the reaction of beryllium hydride with the acid groups in carboxy terminated polybutadiene.

  6. First-principles calculations of niobium hydride formation in superconducting radio-frequency cavities

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Denise C.; Cooley, Lance D.; Seidman, David N.

    2013-09-01

    Niobium hydride is suspected to be a major contributor to degradation of the quality factor of niobium superconducting radio-frequency (SRF) cavities. In this study, we connect the fundamental properties of hydrogen in niobium to SRF cavity performance and processing. We modeled several of the niobium hydride phases relevant to SRF cavities and present their thermodynamic, electronic, and geometric properties determined from calculations based on density-functional theory. We find that the absorption of hydrogen from the gas phase into niobium is exothermic and hydrogen becomes somewhat anionic. The absorption of hydrogen by niobium lattice vacancies is strongly preferred over absorption into interstitial sites. A single vacancy can accommodate six hydrogen atoms in the symmetrically equivalent lowest-energy sites and additional hydrogen in the nearby interstitial sites affected by the strain field: this indicates that a vacancy can serve as a nucleation center for hydride phase formation. Small hydride precipitates may then occur near lattice vacancies upon cooling. Vacancy clusters and extended defects should also be enriched in hydrogen, potentially resulting in extended hydride phase regions upon cooling. We also assess the phase changes in the niobium-hydrogen system based on charge transfer between niobium and hydrogen, the strain field associated with interstitial hydrogen, and the geometry of the hydride phases. The results of this study stress the importance of not only the hydrogen content in niobium, but also the recovery state of niobium for the performance of SRF cavities.

  7. The Study of NADPH-Dependent Flavoenzyme-Catalyzed Reduction of Benzo[1,2-c]1,2,5-oxadiazole N-Oxides (Benzofuroxans

    Directory of Open Access Journals (Sweden)

    Jonas Šarlauskas

    2014-12-01

    Full Text Available The enzymatic reactivity of a series of benzo[1,2-c]1,2,5-oxadiazole N-oxides (benzofuroxans; BFXs towards mammalian single-electron transferring NADPH:cytochrome P-450 reductase (P-450R and two-electron (hydride transferring NAD(PH:quinone oxidoreductase (NQO1 was examined in this work. Since the =N+ (→OO− moiety of furoxan fragments of BFXs bears some similarity to the aromatic nitro-group, the reactivity of BFXs was compared to that of nitro-aromatic compounds (NACs whose reduction mechanisms by these and other related flavoenzymes have been extensively investigated. The reduction of BFXs by both P-450R and NQO1 was accompanied by O2 uptake, which was much lower than the NADPH oxidation rate; except for annelated BFXs, whose reduction was followed by the production of peroxide. In order to analyze the possible quantitative structure-activity relationships (QSARs of the enzymatic reactivity of the compounds, their electron-accepting potency and other reactivity indices were assessed by quantum mechanical methods. In P-450R-catalyzed reactions, both BFXs and NACs showed the same reactivity dependence on their electron-accepting potency which might be consistent with an “outer sphere” electron transfer mechanism. In NQO1-catalyzed two-electron (hydride transferring reactions, BFXs acted as more efficient substrates than NACs, and the reduction efficacy of BFXs by NQO1 was in general higher than by single-electron transferring P-450R. In NQO1-catalyzed reactions, QSARs obtained showed that the reduction efficacy of BFXs, as well as that of NACs, was determined by their electron-accepting potency and could be influenced by their binding mode in the active center of NQO1 and by their global softness as their electronic characteristic. The reductive conversion of benzofuroxan by both flavoenzymes yielded the same reduction product of benzofuroxan, 2,3-diaminophenazine, with the formation of o-benzoquinone dioxime as a putative primary

  8. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated......This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today...... was developed. The parameters milling time, milling intensity, number of balls and form of the alloying metals were investigated. Based on this a final alloying technique for the subsequent preparation of electrode materials was established. The technique comprises milling for 4 hours twice possibly followed...

  9. A REVIEW: THE EFFECT OF OPERATING CONDITIONS AND THERMAL MANAGEMENT ON THE PERFORMANCES OF METAL HYDRIDE HYDROGEN STORAGE TANK

    Directory of Open Access Journals (Sweden)

    Taurista Perdana Syawitri

    2016-12-01

    Full Text Available For safety and operability concerns, the use of metal hydrides to store hydrogen appears to be particularly promising option for alternative energy at present. However, the process of adding, removing and distributing heat during the hydrogen charging/ discharging process is problematic due to the poor effective thermal conductivity of the metal hydride porous bed and the high enthalpies of H2 adsorption/desorption. Therefore, heat transfer is a critical factor affecting the performance of metal hydride hydrogen (MHR storage tanks. Over decade, many researches focused on MHR’s operating conditions and its thermal management to improve its performance.

  10. Predicting formation enthalpies of metal hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.

    2004-01-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formedby chemical reaction between hydrogen...... and metal and for the stable hydrides this is associated with release of heat (#DELTA#H_f ). The more thermodynamically stable the hydride, the larger DHf, and the higher temperature is needed in order to desorphydrogen (reverse reaction) and vice versa. For practical application the temperature needed...

  11. Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.

    Science.gov (United States)

    Jordan, Abraham J; Lalic, Gojko; Sadighi, Joseph P

    2016-08-10

    Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

  12. Crystal structure of gold hydride

    Energy Technology Data Exchange (ETDEWEB)

    Degtyareva, Valentina F., E-mail: degtyar@issp.ac.ru

    2015-10-05

    Highlights: • Volume expansion of metal hydrides is due to the increase in the s-band filling. • AuH structure is similar to that of Hg having one more s electron compared to Au. • Structure stability of both Hg and AuH is governed by the Hume-Rothery rule. - Abstract: A number of transition metal hydrides with close-packed metal sublattices of fcc or hcp structures with hydrogen in octahedral interstitial positions were obtained by the high-pressure-hydrogen technique described by Ponyatovskii et al. (1982). In this paper we consider volume increase of metals by hydrogenation and possible crystal structure of gold hydride in relation with the structure of mercury, the nearest neighbor of Au in the Periodic table. Suggested structure of AuH has a basic tetragonal body-centered cell that is very similar to the mercury structure Hg-t I 2. The reasons of stability for this structure are discussed within the model of Fermi sphere–Brillouin zone interactions.

  13. Fundamental experiments on hydride reorientation in zircaloy

    Science.gov (United States)

    Colas, Kimberly B.

    In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and

  14. Structural characterization of tartrate dehydrogenase: a versatile enzyme catalyzing multiple reactions

    Energy Technology Data Exchange (ETDEWEB)

    Malik, Radhika; Viola, Ronald E. (Toledo)

    2010-10-28

    The first structure of an NAD-dependent tartrate dehydrogenase (TDH) has been solved to 2 {angstrom} resolution by single anomalous diffraction (SAD) phasing as a complex with the intermediate analog oxalate, Mg{sup 2+} and NADH. This TDH structure from Pseudomonas putida has a similar overall fold and domain organization to other structurally characterized members of the hydroxy-acid dehydrogenase family. However, there are considerable differences between TDH and these functionally related enzymes in the regions connecting the core secondary structure and in the relative positioning of important loops and helices. The active site in these complexes is highly ordered, allowing the identification of the substrate-binding and cofactor-binding groups and the ligands to the metal ions. Residues from the adjacent subunit are involved in both the substrate and divalent metal ion binding sites, establishing a dimer as the functional unit and providing structural support for an alternating-site reaction mechanism. The divalent metal ion plays a prominent role in substrate binding and orientation, together with several active-site arginines. Functional groups from both subunits form the cofactor-binding site and the ammonium ion aids in the orientation of the nicotinamide ring of the cofactor. A lysyl amino group (Lys192) is the base responsible for the water-mediated proton abstraction from the C2 hydroxyl group of the substrate that begins the catalytic reaction, followed by hydride transfer to NAD. A tyrosyl hydroxyl group (Tyr141) functions as a general acid to protonate the enolate intermediate. Each substrate undergoes the initial hydride transfer, but differences in substrate orientation are proposed to account for the different reactions catalyzed by TDH.

  15. Kinetics of hydride front in Zircaloy-2 and H release from a fractional hydrided surface

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, M.; Gonzalez-Gonzalez, A.; Moya, J. S.; Remartinez, B.; Perez, S.; Sacedon, J. L. [Instituto de Ciencia de Materiales de Madrid (CSIC), Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain); Iberdrola, Tomas Redondo 3, 28033 Madrid (Spain); Instituto de Ciencia de Materiales de Madrid (CSIC), Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain)

    2009-07-15

    The authors study the hydriding process on commercial nuclear fuel claddings from their inner surface using an ultrahigh vacuum method. The method allows determining the incubation and failure times of the fuel claddings, as well as the dissipated energy and the partial pressure of the desorbed H{sub 2} from the outer surface of fuel claddings during the hydriding process. The correlation between the hydriding dissipated energy and the amount of zirconium hydride (formed at different stages of the hydriding process) leads to a near t{sup 1/2} potential law corresponding to the time scaling of the reaction for the majority of the tested samples. The calibrated relation between energy and hydride thickness allows one to calculate the enthalpy of the {delta}-ZrH{sub 1.5} phase. The measured H{sub 2} desorption from the external surface is in agreement with a proposed kinetic desorption model from the hydrides precipitated at the surface.

  16. Ionic conduction of lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Pilipenko, G.I.; Oparin, D.V.; Zhuravlev, N.A.; Gavrilov, F.F.

    1987-09-01

    Using the electrical-conductivity- and NMR-measurement- methods, the ionic-conduction mechanism is established in stoichiometric lithium hydride single crystals. The activation energies of migration of anion- and cation-vacancies and the formation of Schottky-pair defects are determined. They assume that the mechanisms of self-diffusion and conductivity are different in lithium hydride.

  17. Highly efficient bimetal synergetic catalysis by a multi-wall carbon nanotube supported palladium and nickel catalyst for the hydrogen storage of magnesium hydride.

    Science.gov (United States)

    Yuan, Jianguang; Zhu, Yunfeng; Li, Liquan

    2014-06-25

    A multi-wall carbon nanotube supported Pd and Ni catalyst efficiently catalyzes the hydrogen storage of magnesium hydride prepared by HCS + MM. Excellent hydrogen storage properties were obtained: hydrogen absorption - 6.44 wt% within 100 s at 373 K, hydrogen desorption - 6.41 wt% within 1800 s at 523 K and 6.70 wt% within 400 s at 573 K.

  18. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Submillimeter Spectroscopy of Hydride Molecules

    Science.gov (United States)

    Phillips, T. G.

    1998-05-01

    Simple hydride molecules are of great importance in astrophysics and astrochemistry. Physically they dominate the cooling of dense, warm phases of the ISM, such as the cores and disks of YSOs. Chemically they are often stable end points of chemical reactions, or may represent important intermediate stages of the reaction chains, which can be used to test the validity of the process. Through the efforts of astronomers, physicists, chemists, and laboratory spectroscopists we have an approximate knowledge of the abundance of some of the important species, but a great deal of new effort will be required to achieve the comprehensive and accurate data set needed to determine the energy balance and firmly establish the chemical pathways. Due to the low moment of inertia, the hydrides rotate rapidly and so have their fundamental spectral lines in the submillimeter. Depending on the cloud geometry and temperature profile they may be observed in emission or absorption. Species such as HCl, HF, OH, CH, CH(+) , NH_2, NH_3, H_2O, H_2S, H_3O(+) and even H_3(+) have been detected, but this is just a fraction of the available set. Also, most deduced abundances are not nearly sufficiently well known to draw definitive conclusions about the chemical processes. For example, the most important coolant for many regions, H_2O, has a possible range of deduced abundance of a factor of 1000. The very low submillimeter opacity at the South Pole site will be a significant factor in providing a new capabilty for interstellar hydride spectroscopy. The new species and lines made available in this way will be discussed.

  20. 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

  1. Bipolar Nickel-Metal Hydride Battery Development Project

    Science.gov (United States)

    Cole, John H.

    1999-01-01

    This paper reviews the development of the Electro Energy, Inc.'s bipolar nickel metal hydride battery. The advantages of the design are that each cell is individually sealed, and that there are no external cell terminals, no electrode current collectors, it is compatible with plastic bonded electrodes, adaptable to heat transfer fins, scalable to large area, capacity and high voltage. The design will allow for automated flexible manufacturing, improved energy and power density and lower cost. The development and testing of the battery's component are described. Graphic presentation of the results of many of the tests are included.

  2. Elemental step thermodynamics of various analogues of indazolium alkaloids to obtaining hydride in acetonitrile.

    Science.gov (United States)

    Lei, Nan-Ping; Fu, Yan-Hua; Zhu, Xiao-Qing

    2015-12-21

    A series of analogues of indazolium alkaloids were designed and synthesized. The thermodynamic driving forces of the 6 elemental steps for the analogues of indazolium alkaloids to obtain hydride in acetonitrile were determined using an isothermal titration calorimeter (ITC) and electrochemical methods, respectively. The effects of molecular structure and substituents on the thermodynamic driving forces of the 6 steps were examined. Meanwhile, the oxidation mechanism of NADH coenzyme by indazolium alkaloids was examined using the chemical mimic method. The result shows that the oxidation of NADH coenzyme by indazolium alkaloids in vivo takes place by one-step concerted hydride transfer mechanism.

  3. Hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S [Tampa, FL; Niemann, Michael U [Venice, FL; Goswami, D Yogi [Tampa, FL; Stefanakos, Elias K [Tampa, FL

    2012-04-10

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

  4. Application of Grote-Hynes theory to the reaction catalyzed by thymidylate synthase.

    Science.gov (United States)

    Kanaan, Natalia; Roca, Maite; Tuñón, Iñaki; Martí, Sergio; Moliner, Vicent

    2010-10-28

    A theoretical study of dynamic effects on the rate-limiting step of the thymidylate synthase catalyzed reaction has been carried out by means of Grote-Hynes theory, successfully predicting the values of the recrossing effects for a chemical reaction that involves the transfer of a classical light particle. The transmission coefficients, obtained at 278, 293, 303, and 313 K, are almost invariant and in all cases far from unity, revealing a significant coupling of the environment motions and the reaction coordinate. Nevertheless, their energetic contribution to the activation free energy represents less than 0.50 kcal/mol for each of the four tested temperatures. Calculation of the transmission coefficient for the isotopically labeled hydride transfer has rendered almost the same values, in agreement with the experimentally observed temperature-independent KIEs. Fourier transform of the time-dependent friction kernel at these four temperatures has allowed obtaining the transition-state friction spectra, which present very small dependence with temperature. Their analysis has led to the identification of some key vibrational modes governing the coupling between the reaction coordinate and the protein environment, thus identifying the relevant motions in the active site and obtaining a full picture of the role of each amino acid.

  5. Simple and Efficient Ruthenium-Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen.

    Science.gov (United States)

    Ray, Ritwika; Chandra, Shubhadeep; Maiti, Debabrata; Lahiri, Goutam Kumar

    2016-06-20

    Oxidative transformations utilizing molecular oxygen (O2 ) as the stoichiometric oxidant are of paramount importance in organic synthesis from ecological and economical perspectives. Alcohol oxidation reactions that employ O2 are scarce in homogeneous catalysis and the efficacy of such systems has been constrained by limited substrate scope (most involve secondary alcohol oxidation) or practical factors, such as the need for an excess of base or an additive. Catalytic systems employing O2 as the "primary" oxidant, in the absence of any additive, are rare. A solution to this longstanding issue is offered by the development of an efficient ruthenium-catalyzed oxidation protocol, which enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant and without any base or hydrogen- or electron-transfer agents. Most importantly, a high degree of selectivity during alcohol oxidation has been predicted for complex settings. Preliminary mechanistic studies including (18) O labeling established the in situ formation of an oxo-ruthenium intermediate as the active catalytic species in the cycle and involvement of a two-electron hydride transfer in the rate-limiting step.

  6. Kinetic behaviour of low-Co AB{sub 5}-type metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Tliha, M., E-mail: Mohamed.Tliha@esstt.rnu.tn [Laboratoire de Mecanique, Materiaux et Procedes, ESSTT, 5 Avenue Taha Hussein, 1008 Tunis (Tunisia); Boussami, S.; Mathlouthi, H.; Lamloumi, J. [Laboratoire de Mecanique, Materiaux et Procedes, ESSTT, 5 Avenue Taha Hussein, 1008 Tunis (Tunisia); Percheron-Guegan, A. [Laboratoire de Chimie Metallurgique des Terres Rares, GLVT, 2-8 Rue Henri Dunant 94320, Thiais Cedex (France)

    2010-11-15

    The kinetic behaviour of the LaNi{sub 3.55}Mn{sub 0.4}Al{sub 0.3}Co{sub 0.4}Fe{sub 0.35} metal hydride, used as a negative electrode in the nickel/metal hydride (Ni/MH) batteries, was investigated using electrochemical impedance spectroscopy (EIS) at different state of charge (SOC). Impedance measurements were performed in the frequency range from 50 kHz to 1 mHz. Electrochemical impedance spectrum of the metal hydride electrode was interpreted by an equivalent circuit including the different electrochemical processes taking place on the interface between the MH electrode and the electrolyte. Electrochemical kinetic parameters such as the charge-transfer resistance R{sub tc}, the exchange current density I{sub 0} and the hydrogen diffusion coefficient D{sub H} were determined at different state of charge. The results of EIS measurements indicate that the electrochemical reaction activity of the LaNi{sub 3.55}Mn{sub 0.4}Al{sub 0.3}Co{sub 0.4}Fe{sub 0.35} metal hydride electrode was markedly improved with increasing state of charge (SOC). The transformation {alpha}-{beta} is probably a limiting step in the mechanisms of hydrogenation of metal hydride electrode.

  7. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether.

    Science.gov (United States)

    Andrews, Ian P; Kwon, Ohyun

    2008-12-08

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethyl ethynyl ether using 0.1% palladium(0) catalyst and 1.0 equiv of tributyltin hydride. The product obtained is a mixture of regioisomers that can be carried forward with exclusive reaction of the beta-isomer. This method is highly reproducible; relative to previously reported procedures, it is more economical and involves a more facile purification procedure.

  8. The structure of ([W3Q4X3(dmpe)3]+, Y-) ion pairs (Q = S, Se; X = H, OH, Br; Y = BF4, PF6, dmpe = Me2PCH2CH2PMe2) in dichloromethane solution and the effect of ion-pairing on the kinetics of proton transfer to the hydride cluster [W3S4H3(dmpe)3]+.

    Science.gov (United States)

    Algarra, Andrés G; Basallote, Manuel G; Fernandez-Trujillo, M Jesús; Llusar, Rosa; Safont, Vicent S; Vicent, Cristian

    2006-07-24

    The 1H,19F HOESY spectra of the title compounds in CD2Cl2 solution indicate that the cluster cations form ion pairs with the BF4- and PF6- anions with a well-defined interionic structure that appears to be basically determined essentially by the nature of the X- ligand. For the clusters with X = H and OH, the structure of the ion pairs is such that the counteranion (Y-) and the X- ligands are placed close to each other. However, when the size and electron density of X- increase (X = Br), Y- is forced to move to a different site, far away from X-. The relevance of ion-pairing on the chemistry of these compounds is clearly seen through a decrease in the rate of proton transfer from HCl to the hydride cluster [W3S4H3(dmpe)3]+ in the presence of an excess of BF4-. The kinetic data for this reaction can be rationalized by considering that the ([W3S4H3(dmpe)3]+, BF4-) ion pairs are unproductive in the proton-transfer process. Theoretical calculations indicate that the real behavior can be more complex. Although the cluster can still form adducts with HCl in the presence of BF4-, the structures of the most-stable BF4--containing HCl adducts show H...H distances too large to allow the subsequent release of H2. In addition, the effective concentration of HCl is also reduced because of the formation of adducts as ClH...BF4-. As a consequence of both effects, the proton transfer takes place more slowly than for the case of the dihydrogen-bonded HCl adduct resulting from the unpaired cluster.

  9. Hydrogen storage in complex metal hydrides

    National Research Council Canada - National Science Library

    Bogdanovic, Borislav; Felderhoff, Michael; Streukens, Guido

    2009-01-01

    ...) are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides...

  10. Method of forming metal hydride films

    Science.gov (United States)

    Steinberg, R.; Alger, D. L.; Cooper, D. W. (Inventor)

    1977-01-01

    The substrate to be coated (which may be of metal, glass or the like) is cleaned, both chemically and by off-sputtering in a vacuum chamber. In an ultra-high vacuum system, vapor deposition by a sublimator or vaporizer coats a cooled shroud disposed around the substrate with a thin film of hydride forming metal which getters any contaminant gas molecules. A shutter is then opened to allow hydride forming metal to be deposited as a film or coating on the substrate. After the hydride forming metal coating is formed, deuterium or other hydrogen isotopes are bled into the vacuum system and diffused into the metal film or coating to form a hydride of metal film. Higher substrate temperatures and pressures may be used if various parameters are appropriately adjusted.

  11. Sealed aerospace metal-hydride batteries

    Science.gov (United States)

    Coates, Dwaine

    1992-01-01

    Nickel metal hydride and silver metal hydride batteries are being developed for aerospace applications. There is a growing market for smaller, lower cost satellites which require higher energy density power sources than aerospace nickel-cadmium at a lower cost than space nickel-hydrogen. These include small LEO satellites, tactical military satellites and satellite constellation programs such as Iridium and Brilliant Pebbles. Small satellites typically do not have the spacecraft volume or the budget required for nickel-hydrogen batteries. NiCd's do not have adequate energy density as well as other problems such as overcharge capability and memory effort. Metal hydride batteries provide the ideal solution for these applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems.

  12. Probing the cerium/cerium hydride interface using nanoindentation

    Energy Technology Data Exchange (ETDEWEB)

    Brierley, Martin, E-mail: martin.brierley@awe.co.uk [Atomic Weapons Establishment, Aldermaston, Berkshire RG7 4PR (United Kingdom); University of Manchester, Manchester M13 9PL (United Kingdom); Knowles, John, E-mail: john.knowles@awe.co.uk [Atomic Weapons Establishment, Aldermaston, Berkshire RG7 4PR (United Kingdom)

    2015-10-05

    Highlights: • A disparity exists between the minimum energy and actual shape of a cerium hydride. • Cerium hydride is found to be harder than cerium metal by a ratio of 1.7:1. • A zone of material under compressive stress was identified surrounding the hydride. • No distribution of hardness was apparent within the hydride. - Abstract: A cerium hydride site was sectioned and the mechanical properties of the exposed phases (cerium metal, cerium hydride, oxidised cerium hydride) were measured using nanoindentation. An interfacial region under compressive stress was observed in the cerium metal surrounding a surface hydride that formed as a consequence of strain energy generated by the volume expansion associated with precipitation of the hydride phase.

  13. The Deceptively Simple Thermolysis of Trivalent Permethyltitanocene Derivatives (η5-C5Me5)2TiR. Formation of a Tetramethylfulvene Titanium Compound (η6-C5Me4CH2)(η5-C5Me5)Ti and RH, Catalyzed by Permethyltitanocene Hydride, (η5-C5Me5)2TiH

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.

    1992-01-01

    The complexes Cp*2TiR (Cp* = η5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = η6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by β-hydroge

  14. THE DECEPTIVELY SIMPLE THERMOLYSIS OF TRIVALENT PERMETHYLTITANOCENE DERIVATIVES (ETA-5-C5ME5)2TIR - FORMATION OF A TETRAMETHYLFULVENE TITANIUM COMPOUND (ETA-6-C5ME4CH2)(ETA-5-C5ME5)TI AND RH, CATALYZED BY PERMETHYLTITANOCENE HYDRIDE, (ETA-5-C5ME5)2TIH

    NARCIS (Netherlands)

    LUINSTRA, GA; TEUBEN, JH

    1992-01-01

    The complexes Cp*2TiR (Cp* = eta-5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = eta-6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

  15. The Deceptively Simple Thermolysis of Trivalent Permethyltitanocene Derivatives (η5-C5Me5)2TiR. Formation of a Tetramethylfulvene Titanium Compound (η6-C5Me4CH2)(η5-C5Me5)Ti and RH, Catalyzed by Permethyltitanocene Hydride, (η5-C5Me5)2TiH

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.

    1992-01-01

    The complexes Cp*2TiR (Cp* = η5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = η6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

  16. Destabilization of magnesium hydride through interface engineering

    OpenAIRE

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesium hydride is very stable, which means that hydrogen is released only at elevated temperature. Furthermore, the kinetics of hydrogen sorption is slow, which further hampers the practical use of this...

  17. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.

    2010-01-01

    ,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

  18. Pin-point chemical modification of RNA with diverse molecules through the functionality transfer reaction and the copper-catalyzed azide-alkyne cycloaddition reaction.

    Science.gov (United States)

    Onizuka, Kazumitsu; Shibata, Atsushi; Taniguchi, Yosuke; Sasaki, Shigeki

    2011-05-07

    The internal modification of RNA has been successfully achieved by the functionality transfer reaction (FTR) and following click chemistry with diverse azide compounds. The benefits of the FTR have been demonstrated by its specificity, rapidity, broad applicability, and procedure simplicity. © The Royal Society of Chemistry 2011

  19. Phase Transfer Catalyzed Synthesis of 1, 2-Bis[(3-aryl)-s-triazolo-[3, 4-b]-[1, 3, 4]thiadiazole-6-yl]ethanes

    Institute of Scientific and Technical Information of China (English)

    De Jiang LI; He Qing FU

    2006-01-01

    A series of new 1, 2-bis[(3-aryl)-s-triazolo[3, 4-b]-[1, 3, 4]thiadiazole-6-yl]ethanes were synthesized in 50-82% yield by cyclization of 3-aryl-4-amino-5-mercapto-1, 2, 4-triazole with butanedioic acid in the presence of POC13 and tetrabutylammonium iodide as phase transfer catalyst.

  20. SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

    Science.gov (United States)

    The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

  1. gamma-Zr-Hydride Precipitate in Irradiated Massive delta- Zr-Hydride

    DEFF Research Database (Denmark)

    Warren, M. R.; Bhattacharya, D. K.

    1975-01-01

    During examination of A Zircaloy-2-clad fuel pin, which had been part of a test fuel assembly in a boiling water reactor, several regions of severe internal hydriding were noticed in the upper-plenum end of the pin. Examination of similar fuel pins has shown that hydride of this type is caused...

  2. The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components Delayed Hydride Cracking

    CERN Document Server

    Puls, Manfred P

    2012-01-01

    By drawing together the current theoretical and experimental understanding of the phenomena of delayed hydride cracking (DHC) in zirconium alloys, The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components: Delayed Hydride Cracking provides a detailed explanation focusing on the properties of hydrogen and hydrides in these alloys. Whilst the focus lies on zirconium alloys, the combination of both the empirical and mechanistic approaches creates a solid understanding that can also be applied to other hydride forming metals.   This up-to-date reference focuses on documented research surrounding DHC, including current methodologies for design and assessment of the results of periodic in-service inspections of pressure tubes in nuclear reactors. Emphasis is placed on showing that our understanding of DHC is supported by progress across a broad range of fields. These include hysteresis associated with first-order phase transformations; phase relationships in coherent crystalline metallic...

  3. Niche applications of metal hydrides and related thermal management issues

    Energy Technology Data Exchange (ETDEWEB)

    Lototskyy, M., E-mail: mlototskyy@uwc.ac.za [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa); Satya Sekhar, B. [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa); Muthukumar, P. [Mechanical Department, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Linkov, V.; Pollet, B.G. [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa)

    2015-10-05

    Highlights: • MH H{sub 2} storage, compression & heat management: developments/thermal management. • Thermodynamic criteria for proper selection of MH for different gas phase applications. • Factors influencing on H{sub 2} charge/discharge dynamic performance and energy efficiency. • The improvement of MH heat transfer characteristics is crucial. • Ways of improvement of heat transfer in the MH systems. - Abstract: This short review highlights and discusses the recent developments and thermal management issues related to metal hydride (MH) systems for hydrogen storage, hydrogen compression and heat management (refrigeration, pump and upgrade, etc.). Special attention is paid to aligning the system features with the requirements of the specific application. The considered system features include the MH material, the MH bed on the basis of its corresponding MH container, as well as the layout of the integrated system.

  4. Preliminary development of flaw evaluation procedures for delayed hydride cracking initiation under hydride non-ratcheting conditions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, S.; Cui, J.; Kawa, D.; Shek, G.K.; Scarth, D.A. [Kinectrics Inc., Toronto, Ontario (Canada)

    2006-07-01

    The flaw evaluation procedure for Delayed Hydride Cracking (DHC) initiation currently provided in the CSA Standard N285.8 was developed for hydride ratcheting conditions, in which flaw-tip hydrides do not completely dissolve at peak temperature. Test results have shown that hydrided regions formed under non-ratcheting conditions, in which flaw-tip hydrides completely dissolve at peak temperature, have significantly higher resistance to cracking than those formed under ratcheting conditions. This paper presents some preliminary work on the development of a procedure for the evaluation of DHC initiation for flaws under hydride non-ratcheting conditions. (author)

  5. TRANSFER

    African Journals Online (AJOL)

    “Chemistry Department, Kenyatta University, P. 0. Box 43844 ... harvester (X) [L 2] in a manner consistent with the following Forster equation for long range energy transfer [3-7]. .... sensitive foods, chemical reactors and essences. Recently we ...

  6. [Phase transfer catalyzed bioconversion of penicillin G to 6-APA by immobilized penicillin acylase in recyclable aqueous two-phase systems with light/pH sensitive copolymers].

    Science.gov (United States)

    Jin, Ke-ming; Cao, Xue-jun; Su, Jin; Ma, Li; Zhuang, Ying-ping; Chu, Ju; Zhang, Si-liang

    2008-03-01

    Immobilized penicillin acylase was used for bioconversion of penicillin PG into 6-APA in aqueous two-phase systems consisting of a light-sensitive polymer PNBC and a pH-sensitive polymer PADB. Partition coefficients of 6-APA was found to be about 5.78 in the presence of 1% NaCl. Enzyme kinetics showed that the reaction reached equilibrium at roughly 7 h. The 6-APA mole yields were 85.3% (pH 7.8, 20 degrees C), with about 20% increment as compared with the reaction of single aqueous phase buffer. The partition coefficient of PG (Na) varied scarcely, while that of the product, 6-APA and phenylacetic acid (PA) significantly varied due to Donnan effect of the phase systems and hydrophobicity of the products. The variation of the partition coefficients of the products also affected the bioconversion yield of the products. In the aqueous two-phase systems, the substrate, PG, the products of 6-APA and PA were biased in the top phase, while immobilized penicillin acylase at completely partitioned at the bottom. The substrate and PG entered the bottom phase, where it was catalyzed into 6-APA and PA and entered the top phase. Inhibition of the substrate and products was removed to result in improvement of the product yield, and the immobilized enzyme showed higher efficiency than the immobilized cells and occupied smaller volume. Compared with the free enzyme, immobilized enzyme had greater stability, longer life-time, and was completely partitioned in the bottom phase and recycle. Bioconversion in two-phase systems using immobilized penicillin acylase showed outstanding advantage. The light-sensitive copolymer forming aqueous two-phase systems could be recovered by laser radiation at 488 nm or filtered 450 nm light, while pH-sensitive polymer PADB could be recovered at the isoelectric point (pH 4.1). The recovery of the two copolymers was between 95% and 99%.

  7. Thin-film metal hydrides.

    Science.gov (United States)

    Remhof, Arndt; Borgschulte, Andreas

    2008-12-01

    The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

  8. Efficient Cu-catalyzed atom transfer radical addition reactions of fluoroalkylsulfonyl chlorides with electron-deficient alkenes induced by visible light.

    Science.gov (United States)

    Tang, Xiao-Jun; Dolbier, William R

    2015-03-27

    Fluoroalkylsulfonyl chlorides, R(f)SO2Cl, in which R(f)=CF3, C4F9, CF2H, CH2F, and CH2CF3, are used as a source of fluorinated radicals to add fluoroalkyl groups to electron-deficient, unsaturated carbonyl compounds. Photochemical conditions, using Cu mediation, are used to produce the respective α-chloro-β-fluoroalkylcarbonyl products in excellent yields through an atom transfer radical addition (ATRA) process. Facile nucleophilic replacement of the α-chloro substituent is shown to lead to further diverse functionalization of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Roman Vladimirovich Rozhkov

    2004-12-19

    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 {beta}-hydrogen in the vinylic halide results in {beta}-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the {alpha}-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.

  10. 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.

  11. Structure and mechanism of styrene monooxygenase reductase: new insight into the FAD-transfer reaction.

    Science.gov (United States)

    Morrison, Eliot; Kantz, Auric; Gassner, George T; Sazinsky, Matthew H

    2013-09-03

    The two-component flavoprotein styrene monooxygenase (SMO) from Pseudomonas putida S12 catalyzes the NADH- and FAD-dependent epoxidation of styrene to styrene oxide. In this study, we investigate the mechanism of flavin reduction and transfer from the reductase (SMOB) to the epoxidase (NSMOA) component and report our findings in light of the 2.2 Å crystal structure of SMOB. Upon rapidly mixing with NADH, SMOB forms an NADH → FADox charge-transfer intermediate and catalyzes a hydride-transfer reaction from NADH to FAD, with a rate constant of 49.1 ± 1.4 s(-1), in a step that is coupled to the rapid dissociation of NAD(+). Electrochemical and equilibrium-binding studies indicate that NSMOA binds FADhq ∼13-times more tightly than SMOB, which supports a vectoral transfer of FADhq from the reductase to the epoxidase. After binding to NSMOA, FADhq rapidly reacts with molecular oxygen to form a stable C(4a)-hydroperoxide intermediate. The half-life of apoSMOB generated in the FAD-transfer reaction is increased ∼21-fold, supporting a protein-protein interaction between apoSMOB and the peroxide intermediate of NSMOA. The mechanisms of FAD dissociation and transport from SMOB to NSMOA were probed by monitoring the competitive reduction of cytochrome c in the presence and absence of pyridine nucleotides. On the basis of these studies, we propose a model in which reduced FAD binds to SMOB in equilibrium between an unreactive, sequestered state (S state) and more reactive, transfer state (T state). The dissociation of NAD(+) after the hydride-transfer reaction transiently populates the T state, promoting the transfer of FADhq to NSMOA. The binding of pyridine nucleotides to SMOB-FADhq shifts the FADhq-binding equilibrium from the T state to the S state. Additionally, the 2.2 Å crystal structure of SMOB-FADox reported in this work is discussed in light of the pyridine nucleotide-gated flavin-transfer and electron-transfer reactions.

  12. High H- ionic conductivity in barium hydride

    Science.gov (United States)

    Verbraeken, Maarten C.; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T. S.

    2015-01-01

    With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H-) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm-1 at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

  13. Thermodynamic diagnosis of the properties and mechanism of dihydropyridine-type compounds as hydride source in acetonitrile with "Molecule ID Card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Tan, Yue; Cao, Chao-Tun

    2010-02-11

    A series of 45 dihydropyridine-type organic compounds as hydride source were designed and synthesized. The thermodynamic driving forces (defined as enthalpy changes or redox potentials in this work) of the dihydropyridines to release hydride anions, hydrogen atoms (hydrogen for short), and electrons in acetonitrile, the thermodynamic driving forces of the radical cations of the dihydropyridines to release protons and hydrogens in acetonitrile, and the thermodynamic driving forces of the neutral pyridine-type radicals of the dihydropyridines to release electron in acetonitrile were determined by using titration calorimetry and electrochemical methods. The rates and activation parameters of hydride transfer from the dihydropyridines to acridinium perclorate, a well-known hydride acceptor, were determined by using UV-vis absorption spectroscopy technique. The relationship between the thermodynamic driving forces and kinetic rate of the hydride transfer was examined. Thermodynamic characteristic graph (TCG) of the dihydropyridines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose or predict the characteristic chemical properties of the dihydropyridines and their various reaction intermediates. The mechanism of hydride transfer from the dihydropyridines to acridinium perclorate was diagnosed and elucidated by using the determined thermodynamic parameters and the activation parameters.

  14. Iodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reaction conditions.

    Science.gov (United States)

    Jereb, Marjan; Vražič, Dejan

    2013-03-28

    Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under solvent-free reaction conditions. Variously substituted 1,1,1',1'-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel-Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C-H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.

  15. Mechanism of H2 Production by Models for the [NiFe]-Hydrogenases: Role of Reduced Hydrides.

    Science.gov (United States)

    Ulloa, Olbelina A; Huynh, Mioy T; Richers, Casseday P; Bertke, Jeffery A; Nilges, Mark J; Hammes-Schiffer, Sharon; Rauchfuss, Thomas B

    2016-07-27

    The intermediacy of a reduced nickel-iron hydride in hydrogen evolution catalyzed by Ni-Fe complexes was verified experimentally and computationally. In addition to catalyzing hydrogen evolution, the highly basic and bulky (dppv)Ni(μ-pdt)Fe(CO)(dppv) ([1](0); dppv = cis-C2H2(PPh2)2) and its hydride derivatives have yielded to detailed characterization in terms of spectroscopy, bonding, and reactivity. The protonation of [1](0) initially produces unsym-[H1](+), which converts by a first-order pathway to sym-[H1](+). These species have C1 (unsym) and Cs (sym) symmetries, respectively, depending on the stereochemistry of the octahedral Fe site. Both experimental and computational studies show that [H1](+) protonates at sulfur. The S = 1/2 hydride [H1](0) was generated by reduction of [H1](+) with Cp*2Co. Density functional theory (DFT) calculations indicate that [H1](0) is best described as a Ni(I)-Fe(II) derivative with significant spin density on Ni and some delocalization on S and Fe. EPR spectroscopy reveals both kinetic and thermodynamic isomers of [H1](0). Whereas [H1](+) does not evolve H2 upon protonation, treatment of [H1](0) with acids gives H2. The redox state of the "remote" metal (Ni) modulates the hydridic character of the Fe(II)-H center. As supported by DFT calculations, H2 evolution proceeds either directly from [H1](0) and external acid or from protonation of the Fe-H bond in [H1](0) to give a labile dihydrogen complex. Stoichiometric tests indicate that protonation-induced hydrogen evolution from [H1](0) initially produces [1](+), which is reduced by [H1](0). Our results reconcile the required reductive activation of a metal hydride and the resistance of metal hydrides toward reduction. This dichotomy is resolved by reduction of the remote (non-hydride) metal of the bimetallic unit.

  16. Lattice contraction in photochromic yttrium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter, E-mail: jepe@ife.no; Mongstad, Trygve T.; You, Chang Chuan; Karazhanov, Smagul

    2013-12-15

    Highlights: •Photochromic yttrium hydride films (YH:O) were prepared by reactive sputtering. •Black and transparent YH:O films were studied by time-resolved synchrotron XRD. •Both YH:O samples showed a lattice contraction upon illumination. •Also exposure to the X-ray beam itself results in a lattice contraction. -- Abstract: A strong photochromic effect was recently discovered in thin films of oxygen-containing yttrium hydride taking place at room temperature and reacting to ultraviolet and visible light. In this paper, we report on a lattice contraction upon illumination observed for thin-film samples of photochromic yttrium hydride, recorded by time-resolved X-ray diffraction using synchrotron radiation. The time dependence of the lattice contraction is consistent with the observed photochromic response of the samples.

  17. Atom probe analysis of titanium hydride precipitates.

    Science.gov (United States)

    Takahashi, J; Kawakami, K; Otsuka, H; Fujii, H

    2009-04-01

    It is expected that the three-dimensional atom probe (3DAP) will be used as a tool to visualize the atomic scale of hydrogen atoms in steel is expected, due to its high spatial resolution and very low detection limit. In this paper, the first 3DAP analysis of titanium hydride precipitates in metal titanium is reported in terms of the quantitative detection of hydrogen. FIB fabrication techniques using the lift-out method have enabled the production of needle tips of hydride precipitates, of several tens of microns in size, within a titanium matrix. The hydrogen concentration estimated from 3DAP analysis was slightly smaller than that of the hydride phase predicted from the phase diagram. We discuss the origin of the difference between the experimental and predicted values and the performance of 3DAP for the quantitative detection of hydrogen.

  18. Hydrogen storage in complex metal hydrides

    Directory of Open Access Journals (Sweden)

    BORISLAV BOGDANOVIĆ

    2009-02-01

    Full Text Available Complex metal hydrides such as sodium aluminohydride (NaAlH4 and sodium borohydride (NaBH4 are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides. The most important point for a wide application of these materials is the reversibility under moderate technical conditions. At present, only NaAlH4 has favourable thermodynamic properties and can be employed as a thermally reversible means of hydrogen storage. By contrast, NaBH4 is a typical non- -reversible complex metal hydride; it reacts with water to produce hydrogen.

  19. Light metal hydrides and complex hydrides for hydrogen storage.

    Science.gov (United States)

    Schüth, F; Bogdanović, B; Felderhoff, M

    2004-10-21

    The availability of feasible methods for hydrogen storage is one of the key-maybe the key-requirements for the large scale application of PEM fuel cells in cars. There are in principle four different approaches, i.e. cryostorage in liquid form, high pressure storage, storage in the form of a chemical compound which is converted to hydrogen by on-board reforming, or reversible chemical storage in different kinds of storage materials. New developments in the field of chemical storage make such systems attractive compared to the other options. This review will discuss the different possibilities for chemical storage of hydrogen and the focus on the presently most advanced system with respect to storage capacity and kinetics, i.e. catalyzed alanates, especially NaAlH(4).

  20. Investigations of the structural stability of metal hydride composites by in-situ neutron imaging

    Science.gov (United States)

    Herbrig, Kai; Pohlmann, Carsten; Gondek, Łukasz; Figiel, Henryk; Kardjilov, Nikolay; Hilger, André; Manke, Ingo; Banhart, John; Kieback, Bernd; Röntzsch, Lars

    2015-10-01

    Metal hydride composites (MHC) with expanded natural graphite (ENG) exhibiting enhanced thermal conductivity and reduced porosity compared to metal hydride powders can enable a reversible, compact and safe way for hydrogen storage. In this study, neutron imaging during cyclic hydrogenation was utilized to investigate the structural stability and the spatial-temporal hydrogen concentration of application-oriented MHC with 40 mm in diameter compared to a loose metal hydride powder. In particular, swelling and shrinking effects of a radially confined MHC which could freely expand upwards were studied. It was found that the loose powder bed was easily torn apart during dehydrogenation, which leads to increased thermal resistance within the hydride bed. In contrast, the thermal resistance between MHC and container wall was minimized since the initial gap closes during initial hydrogenation and does not reopen thereafter. Further cyclic hydrogenation caused MHC volume changes, i.e. an almost reversible swelling/shrinking (so-called ;MHC breathing;). Moreover, neutron imaging allowed for the observation of reaction fronts within the MHC and the powder bed that are governed by the heat transfer.

  1. P-hydrogen-substituted 1,3,2-diazaphospholenes: molecular hydrides.

    Science.gov (United States)

    Burck, Sebastian; Gudat, Dietrich; Nieger, Martin; Du Mont, Wolf-Walther

    2006-03-29

    P-Hydrogen-substituted 1,3,2-diazaphospholenes 1 were prepared by an improved procedure from diazadienes and were characterized by spectroscopy and in one case by X-ray diffraction. A unique hydride-type reactivity of the P-H bonds was documented by extensive reactivity studies. Aldehydes and ketones were readily reduced to diazaphospholene derivatives of the corresponding alcohols, with alkyl-substituted ketones being converted at much lower rates than aldehydes or diaryl ketones. Reactions with the tetrachlorides of group 14 elements proceeded via hydride/chloride metathesis to give either partially chlorinated derivatives EH(n)Cl(4-n) (n = 0-3 for E = C, Si) or HCl and phosphenium salts 16c[ECl3] (for E = Ge, Sn) which were characterized by spectroscopic and X-ray diffraction studies. Tin dichloride was readily reduced to the element. Reactions of 1c with the P-chloro-diazaphospholene 3c and the salt 16c[OTf] allowed the first experimental detection of intermolecular exchange of a hydride, rather than a proton, between phosphine derivatives. Computational studies indicated that the hydride transfer between 1c and the cation 16c involves a transient H-bridged species with bonding properties similar to those of B2H7-. The preference for the formation of these bridged intermediates over P-P bonded phosphenium-phosphine adducts is attributed to the low electrophilicity of the diazaphospholenium cations and characterizes a novel reaction mode for phosphenium ions.

  2. The Application of Transient-State Kinetic Isotope Effects to the Resolution of Mechanisms of Enzyme-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Harvey F. Fisher

    2013-07-01

    Full Text Available Much of our understanding of the mechanisms of enzyme-catalyzed reactions is based on steady-state kinetic studies. Experimentally, this approach depends solely on the measurement of rates of free product appearance (d[P]/dt, a mechanistically and mathematically complex entity. Despite the ambiguity of this observed parameter, the method’s success is due in part to the elaborate rigorously derived algebraic theory on which it is based. Transient-state kinetics, on the other hand, despite its ability to observe the formation of intermediate steps in real time, has contributed relatively little to the subject due in, some measure, to the lack of such a solid mathematical basis. Here we discuss the current state of existing transient-state theory and the difficulties in its realistic application to experimental data. We describe a basic analytic theory of transient-state kinetic isotope effects in the form of three novel fundamental rules. These rules are adequate to define an extended mechanism, locating the isotope-sensitive step and identifying missing steps from experimental data. We demonstrate the application of these rules to resolved component time courses of the phenylalanine dehydrogenase reaction, extending the previously known reaction by one new prehydride transfer step and two new post hydride transfer steps. We conclude with an assessment of future directions in this area.

  3. Separation/preconcentration of ultra-trace levels of inorganic Sb and Se from different sample matrices by charge transfer sensitized ion-pairing using ultrasonic-assisted cloud point extraction prior to their speciation and determination by hydride generation AAS.

    Science.gov (United States)

    Altunay, Nail; Gürkan, Ramazan

    2016-10-01

    In the existing study, a new, simple and low cost process for separation/preconcentration of ultra-trace level of inorganic Sb and Se from natural waters, beverages and foods using ultrasonic-assisted cloud point extraction (UA-CPE) prior to their speciation and determination by hydride generation AAS, is proposed. The process is based on charge transfer sensitized complex formations of Sb(III) and Se(IV) with 3-amino-7-dimethylamino-2-methylphenazine hydrochloride (Neutral red, NRH(+)) in presence of pyrogallol and cetyltrimethylammonium bromide (CTAB) as both sensitivity enhancement and counter ion at pH 6.0. Under the optimized reagent conditions, the calibration curves were highly linear in the ranges of 8-300ngL(-1) and 12-250ngL(-1) (r(2)≥0.993) for Se(IV) and Sb(III), respectively. The limits of detection were 2.45 and 3.60ngL(-1) with sensitivity enhancement factors of 155 and 120, respectively. The recovery rate was higher than 96% with a relative standard deviation lower than 5.3% for five replicate measurements of 25, 75 and 150ngL(-1) Se(IV) and Sb(III), respectively. The method was validated by analysis of two certified reference materials (CRMs), and was successfully applied to the accurate and reliable speciation and determination of the contents of total Sb/Sb(III), and total Se/Se(IV) after UA-CPE of the pretreated sample matrices with and without pre-reduction with a mixture of l-cysteine and tartaric acid. Their Sb(V) and Se(VI) contents were calculated from the differences between total Sb and Sb(III) and/or total Se and Se(IV) levels.

  4. Evidence of stress-induced hydrogen ordering in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Steuwer, A. [FaME38 at the ESRF-ILL, 6 rue J Horowitz, 38042 Grenoble (France); ESS Scandinavia, University of Lund, Stora Algatan 4, 22350 Lund (Sweden)], E-mail: steuwer@ill.fr; Santisteban, J.R. [Centro Atomico Bariloche, CNEA, San Carlos de Bariloche (Argentina); Preuss, M. [University of Manchester, Grosvenor Street, Manchester M1 7HS (United Kingdom); Peel, M.J.; Buslaps, T. [European Synchrotron Radiation Facility, 6 rue J Horowitz, 38042 Grenoble (France); Harada, M. [R and D Section, Chofu-Kita Plant, Kobe Special Tube Co, Shimonoseki 752-0953 (Japan)

    2009-01-15

    The formation of hydrides in zirconium alloys significantly affects their mechanical properties and is considered to play a critical role in their failure mechanisms, yet relatively little is known about the micromechanical behavior of hydrides in the bulk. This paper presents the result of in situ uniaxial mechanical tensioning experiments on hydrided zircaloy-2 and zircaloy-4 specimens using energy-dispersive synchrotron X-ray diffraction, which suggests that a stress-induced transformation of the {delta}-hydride to {gamma}-hydride via ordering of the hydrogen atoms occurs, akin to a Snoek-type relaxation. Subsequent annealing was found to reverse the ordering phenomenon.

  5. Arrested α-hydride migration activates a phosphido ligand for C–H insertion

    Energy Technology Data Exchange (ETDEWEB)

    Hickey, Anne K. [Indiana Univ., Bloomington, IN (United States); Muñoz, Salvador B. [Indiana Univ., Bloomington, IN (United States); Lutz, Sean A. [Indiana Univ., Bloomington, IN (United States); Pink, Maren [Indiana Univ., Bloomington, IN (United States); Chen, Chun-Hsing [Indiana Univ., Bloomington, IN (United States); Smith, Jeremy M. [Indiana Univ., Bloomington, IN (United States)

    2016-12-05

    Bulky tris(carbene)borate ligands provide access to high spin iron(II) phosphido complexes. The complex PhB(MesIm)3FeP(H)Ph is thermally unstable, and we observed [PPh] group insertion into a C–H bond of the supporting ligand. An arrested α-hydride migration mechanism suggests increased nucleophilicity of the phosphorus atom facilitates [PPh] group transfer reactivity.

  6. A New Palladium-Catalyzed Phenyl-Alkene Bond Formation

    Directory of Open Access Journals (Sweden)

    René Roy

    2002-05-01

    Full Text Available A new method of palladium-catalyzed phenyl-alkene bond formation is reported. This reaction involves transfer of all three phenyl groups from triphenylantimony onto alkenes containing allylic protons.

  7. Orientation towards asymmetric transfer hydrogenation of ketones catalyzed by (pyrazolyl)ethyl)pyridine Fe(II) and Ni(II) complexes

    Science.gov (United States)

    Magubane, Makhosazane N.; Alam, Mohd Gulfam; Ojwach, Stephen O.; Munro, Orde Q.

    2017-05-01

    Compounds 2-[1-(3,5-dimethylpyrazol-1-yl)ethyl]pyridine (L1) and 2-[1-(3,5-diphenylpyrazol-1-yl)ethyl]pyridine (L2) were obtained in a three-step procedure which involved the reduction of acetylpyridine using NaBH4, chlorination of the alcohol intermediate using SOCl2 and subsequent reaction with appropriate pyrazoles. Reactions of L1 and L2 with Ni(II) and Fe(II) halides produced the respective complexes Ni(L1)Br2 (1), Ni(L1)Cl2 (2), Fe(L1)Cl2 (3) and Ni(L2)Br2 (4) as racemic mixtures in moderate yields. The molecular structures of complexes 1 and 4 are dinuclear and mononuclear respectively. All the complexes (1-4) formed active catalysts for the transfer hydrogenation of ketones (THK) in 2-propanol at 82 °C affording conversions of 58%-84% within 48 h. The influence of catalyst structure, reaction conditions and identity of ketone substrates in the TH reactions have been successfully established.

  8. Hydride formation on deformation twin in zirconium alloy

    Science.gov (United States)

    Kim, Ju-Seong; Kim, Sung-Dae; Yoon, Jonghun

    2016-12-01

    Hydrides deteriorate the mechanical properties of zirconium (Zr) alloys used in nuclear reactors. Intergranular hydrides that form along grain boundaries have been extensively studied due to their detrimental effects on cracking. However, it has been little concerns on formation of Zr hydrides correlated with deformation twins which is distinctive heterogeneous nucleation site in hexagonal close-packed metals. In this paper, the heterogeneous precipitation of Zr hydrides at the twin boundaries was visualized using transmission electron microscopy. It demonstrates that intragranular hydrides in the twinned region precipitates on the rotated habit plane by the twinning and intergranular hydrides precipitate along the coherent low energy twin boundaries independent of the conventional habit planes. Interestingly, dislocations around the twin boundaries play a substantial role in the nucleation of Zr hydrides by reducing the misfit strain energy.

  9. 逆相转移催化合成葵花籽油蔗糖酯%Synthesis of sunflower oil sucrose ester catalyzed by inverse phase - transfer catalyst

    Institute of Scientific and Technical Information of China (English)

    樊国栋; 康丽; 林振宇

    2012-01-01

    Using water solvent method, sunflower oil sucrose ester was synthesized by inverse phase -transfer catalyst DMAP with sucrose and fatty acid methyl ester prepared by ester - exchange method in the presence of basic catalyst from sunflower oil and methanol. The effects of molar ratio of fatty acids methyl ester to sucrose, catalyst dosage, reaction temperature and reaction time were studied. The results showed that the optimal conditions were as follows; molar ratio of fatty acids methyl ester to sucrose 2.5:1, catalyst dosage 4% , reaction temperature 85 °C and reaction time 7 h. Under the optimal conditions, the conversion rate of sunflower oil fatty acid methyl ester could reach 65. 32%. The final product had good surface activity, the critical micelle concentration(CMC) was 6. 5 g/L, surface tension was 27.41 mN/ m, emulsifying power was 79s, water count was 7. 2 mL, HLB was 10. 1 and iodine value was 126. 9 gI/ 100 g.%先由食用葵花籽油和甲醇在碱性催化剂条件下酯交换反应制得脂肪酸甲酯,然后脂肪酸甲酯与蔗糖通过水溶剂法,以逆相转移催化剂DMAP催化制备蔗糖脂肪酸酯.通过对酯糖摩尔比、催化剂用量、反应温度、反应时间进行考察,确定最佳合成条件为:酯糖摩尔比2.5∶1,催化剂用量4%,反应温度 85℃,反应时间7h.在最佳合成条件下,葵花籽油脂肪酸甲酯的转化率高达65.32%,所得产品具有良好的表面活性,其临界胶束质量浓度(CMC)为6.5 g/L,表面张力为27.41 mN/m,乳化力为79 s,浊点指数为7.2 mL,HLB值为10.1,碘值(Ⅰ)为126.9 g/100 g.

  10. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form,

  11. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  12. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  13. Development of a metal hydride refrigeration system as an exhaust gas-driven automobile air conditioner

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Feng; Chen, Jiangping; Chen, Zhijiu [Institute of Refrigeration and Cryogenics Engineering, Shanghai Jiaotong University, Shanghai 200030 (China); Lu, Manqi; Yang, Ke [Engineering Center, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, Liaoning Province 110016 (China); Zhou, Yimin [Research Center, Zhejiang Yinlun Machinery Co. Ltd., Tiantai County, Zhejiang Province 317200 (China)

    2007-10-15

    Aiming at developing exhaust gas-driven automobile air conditioners, two types of systems varying in heat carriers were preliminarily designed. A new hydride pair LaNi{sub 4.61}Mn{sub 0.26}Al{sub 0.13}/La{sub 0.6}Y{sub 0.4}Ni{sub 4.8}Mn{sub 0.2} was developed working at 120-200 C/20-50 C/-10-0 C. P-C isotherms and reaction kinetics were tested. Reaction enthalpy, entropy and theoretical cycling coefficient of performance (COP) were deducted from Van't-Hoff diagram. Test results showed that the hydride pair has flat plateau slopes, fast reaction dynamics and small hystereses; the reaction enthalpy of the refrigeration hydride is -27.1 kJ/mol H{sub 2} and system theoretical COP is 0.711. Mean particle sizes during cycles were verified to be an intrinsic property affected by constitution, heat treatment and cycle numbers rather than initial grain sizes. Based on this work pair, cylindrical reactors were designed and a function proving metal hydride intermittent refrigeration system was constructed with heat conducting oil as heat source and water as heat sink. The reactor equivalent thermal conductivity is merely 1.3 W/(m K), which still has not meet practical requirement. Intermittent refrigeration cycles were achieved and the average cooling power is 84.6 W at 150 C/30 C/0 C with COP being 0.26. The regulations of cycling performance and minimum refrigeration temperature (MRT) were determined by altering heat source temperature. Results showed that cooling power and system COP increase while MRT decreases with the growth of heat source temperature. This study develops a new hydride pair and confirms its application in automobile refrigeration systems, while their heat transfer properties still need to be improved for better performance. (author)

  14. Mechanism of n-butane hydrogenolysis promoted by Ta-hydrides supported on silica

    KAUST Repository

    Pasha, Farhan Ahmad

    2014-06-06

    The mechanism of hydrogenolysis of alkanes, promoted by Ta-hydrides supported on silica via 2 ≡ Si-O- bonds, has been studied with a density functional theory (DFT) approach. Our study suggests that the initial monohydride (≡ Si-O-)2Ta(III)H is rapidly trapped by molecular hydrogen to form the more stable tris-hydride (≡ Si-O-) 2Ta(V)H3. Loading of n-butane to the Ta-center occurs through C-H activation concerted with elimination of molecular hydrogen (σ-bond metathesis). Once the Ta-alkyl species is formed, the C-C activation step corresponds to a β-alkyl transfer to the metal with elimination of an olefin. According to these calculations, an α-alkyl transfer to the metal to form a Ta-carbene species is of higher energy. The olefins formed during the C-C activation step can be rapidly hydrogenated by both mono- and tris-Ta-hydride species, making the overall process of alkane cracking thermodynamically favored. © 2014 American Chemical Society.

  15. Muon Catalyzed Fusion

    Science.gov (United States)

    Armour, Edward A.G.

    2007-01-01

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

  16. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  17. Direct passivation of hydride-terminated silicon (100) surfaces by free-radically tethered polymer brushes.

    Science.gov (United States)

    Moran, Isaac W; Carter, Kenneth R

    2009-08-18

    A simple and effective means for passivating crystalline silicon is reported by the use of free-radical polymerization (FRP) to directly graft polymer chains to a hydride-terminated surface (Si-H). Complete surface coverage and passivation was achieved in approximately 24 h at 60 degrees C or 30 min at 90 degrees C. Mechanistic studies determined that chain attachment followed a hydride-transfer-based grafting-to mechanism. The grafting process is compatible with a variety of monomers and was used to assemble polymer brush layers (2-12 nm thick), with grafting densities ranging from 0.02 to 0.65 chains/nm2 rivaling densities typically obtained by grafting-from scenarios. This new passivation route provides a uniquely accessible means to covalently anchor dense polymer brushes to silicon surfaces without the need for functionalization of the polymer chain ends or the substrate.

  18. Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

    Science.gov (United States)

    de Rango, P.; Marty, P.; Fruchart, D.

    2016-02-01

    The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

  19. Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems

    Science.gov (United States)

    Ward, Patrick A.; Corgnale, Claudio; Teprovich, Joseph A.; Motyka, Theodore; Hardy, Bruce; Sheppard, Drew; Buckley, Craig; Zidan, Ragaiy

    2016-04-01

    Recently, there has been increasing interest in thermal energy storage (TES) systems for concentrated solar power (CSP) plants, which allow for continuous operation when sunlight is unavailable. Thermochemical energy storage materials have the advantage of much higher energy densities than latent or sensible heat materials. Furthermore, thermochemical energy storage systems based on metal hydrides have been gaining great interest for having the advantage of higher energy densities, better reversibility, and high enthalpies. However, in order to achieve higher efficiencies desired of a thermal storage system by the US Department of Energy, the system is required to operate at temperatures >600 °C. Operation at temperatures >600 °C presents challenges including material selection, hydrogen embrittlement and permeation of containment vessels, appropriate selection of heat transfer fluids, and cost. Herein, the technical difficulties and proposed solutions associated with the use of metal hydrides as TES materials in CSP applications are discussed and evaluated.

  20. Trimethylsilyl-Substituted Hydroxycyclopentadienyl Ruthenium Hydrides as Benchmarks to Probe Ligand and Metal Effects on the Reactivity of Shvo Type Complexes.

    Science.gov (United States)

    Casey, Charles P; Guan, Hairong

    2012-01-01

    The bis(trimethylsilyl)-substituted hydroxycyclopentadienyl ruthenium hydride [2,5-(SiMe(3))(2)-3,4-(CH(2)OCH(2))(η(5)-C(4)COH)]Ru(CO)(2)H (10) is an efficient catalyst for hydrogenation of aldehydes and ketones. Because 10 transfers hydrogen rapidly to aldehydes and ketones and because it does not form an inactive bridging hydride during reaction, hydrogenation of aldehydes and ketones can be performed at room temperature under relatively low hydrogen pressure (3 atm); this is a significant improvement compared with previously developed Shvo type catalysts. Kinetic and (2)H NMR spectroscopic studies of the stoichiometric reduction of aldehydes and ketones by 10 established a two-step process for the hydrogen transfer: (1) rapid and reversible hydrogen bond formation between OH of 10 and the oxygen of the aldehyde or ketone, (2) followed by slow transfer of both proton and hydride from 10 to the aldehyde or ketone. The stoichiometric and catalytic activities of complex 10 are compared to those of other Shvo type ruthenium hydrides and related iron hydrides.

  1. Numerical study of a magnesium hydride tank

    Science.gov (United States)

    Delhomme, Baptiste; de Rango, Patricia; Marty, Philippe

    2012-11-01

    Hydrogen storage in metal hydride tanks (MHT) is a very promising solution. Several experimental tanks, studied by different teams, have already proved the feasibility and the interesting performances of this solution. However, in much cases, an optimization of tank geometry is still needed in order to perform fast hydrogen loading. The development of efficient numerical tools is a key issue for MHT design and optimization. We propose a simple model representing a metal hydride tank exchanging its heat of reaction with a thermal fluid flow. In this model, the radial and axial discretisations have been decoupled by using Matlab® one-dimensional tools. Calculations are compared to experimental results obtained in a previous study. A good agreement is found for the loading case. The discharging case shows some discrepancies, which are discussed in this paper.

  2. Nickel metal hydride LEO cycle testing

    Science.gov (United States)

    Lowery, Eric

    1995-01-01

    The George C. Marshall Space Flight Center is working to characterize aerospace AB5 Nickel Metal Hydride (NiMH) cells. The cells are being evaluated in terms of storage, low earth orbit (LEO) cycling, and response to parametric testing (high rate charge and discharge, charge retention, pulse current ability, etc.). Cells manufactured by Eagle Picher are the subjects of the evaluation. There is speculation that NiMH cells may become direct replacements for current Nickel Cadmium cells in the near future.

  3. Storing hydrogen in the form of light alloy hydrides

    Science.gov (United States)

    Freund, E.; Gillerm, C.

    1981-01-01

    Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

  4. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    Science.gov (United States)

    Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

    2014-12-23

    In this review, we discuss the evolution of localized surface plasmon resonance and surface plasmon resonance hydrogen sensors based on nanostructured metal hydrides, which has accelerated significantly during the past 5 years. We put particular focus on how, conceptually, plasmonic resonances can be used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and at the single-nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes in the quest to develop efficient solid-state hydrogen storage materials with fast response times, reasonable thermodynamics, and acceptable long-term stability. Therefore, a brief introduction to the thermodynamics of metal hydride formation is also given. However, plasmonic hydrogen sensors not only are of academic interest as research tool in materials science but also are predicted to find more practical use as all-optical gas detectors in industrial and medical applications, as well as in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier. Therefore, the wide range of different plasmonic hydrogen sensor designs already available is reviewed together with theoretical efforts to understand their fundamentals and optimize their performance in terms of sensitivity. In this context, we also highlight important challenges to be addressed in the future to take plasmonic hydrogen sensors from the laboratory to real applications in devices, including poisoning/deactivation of the active materials, sensor lifetime, and cross-sensitivity toward other gas species.

  5. Gold-catalyzed naphthalene functionalization

    Directory of Open Access Journals (Sweden)

    Iván Rivilla

    2011-05-01

    Full Text Available The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenylimidazol-2-ylidene, M = Cu, 1a; M = Au, 1b, in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethylphenyl, catalyze the transfer of carbene groups: C(RCO2Et (R = H, Me from N2C(RCO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed.

  6. The influence of extra framework aluminium on H-fak catalyzed cracking of light alkanes

    NARCIS (Netherlands)

    Narbeshuber, T.; Narbeshuber, T.F.; Brait, A.; Brait, A.; Seshan, Kulathuiyer; Lercher, J.A.

    1996-01-01

    The conversion of light linear and branched alkanes on two faujasite samples containing different concentrations of free Brønsted acid sites and extraframework alumina (EFAL) was studied between 733 K and 813 K. Protolytic cracking and bimolecular hydride transfer proceeded solely on Brønsted acid

  7. The influence of extraframework aluminum on H-FAU catalyzed cracking of light alkanes

    NARCIS (Netherlands)

    Narbeshuber, T.F.; Brait, A.; Seshan, K.; Lercher, J.A.

    1996-01-01

    The conversion of light linear and branched alkanes on two faujasite samples containing different concentrations of free Brønsted acid sites and extraframework alumina (EFAL) was studied between 733 K and 813 K. Protolytic cracking and bimolecular hydride transfer proceeded solely on Brønsted acid s

  8. Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

    KAUST Repository

    Guo, Lin

    2016-06-13

    A new and efficient nickel-catalyzed alkylation of CAr-O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various Csp2-Csp3 bonds through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

  9. A nickel hydride complex in the active site of methyl-coenzyme m reductase: implications for the catalytic cycle.

    Science.gov (United States)

    Harmer, Jeffrey; Finazzo, Cinzia; Piskorski, Rafal; Ebner, Sieglinde; Duin, Evert C; Goenrich, Meike; Thauer, Rudolf K; Reiher, Markus; Schweiger, Arthur; Hinderberger, Dariush; Jaun, Bernhard

    2008-08-20

    Methanogenic archaea utilize a specific pathway in their metabolism, converting C1 substrates (i.e., CO2) or acetate to methane and thereby providing energy for the cell. Methyl-coenzyme M reductase (MCR) catalyzes the key step in the process, namely methyl-coenzyme M (CH3-S-CoM) plus coenzyme B (HS-CoB) to methane and CoM-S-S-CoB. The active site of MCR contains the nickel porphinoid F430. We report here on the coordinated ligands of the two paramagnetic MCR red2 states, induced when HS-CoM (a reversible competitive inhibitor) and the second substrate HS-CoB or its analogue CH3-S-CoB are added to the enzyme in the active MCR red1 state (Ni(I)F430). Continuous wave and pulse EPR spectroscopy are used to show that the MCR red2a state exhibits a very large proton hyperfine interaction with principal values A((1)H) = [-43,-42,-5] MHz and thus represents formally a Ni(III)F430 hydride complex formed by oxidative addition to Ni(I). In view of the known ability of nickel hydrides to activate methane, and the growing body of evidence for the involvement of MCR in "reverse" methanogenesis (anaerobic oxidation of methane), we believe that the nickel hydride complex reported here could play a key role in helping to understand both the mechanism of "reverse" and "forward" methanogenesis.

  10. Significantly improved electrochemical hydrogen storage properties of magnesium nickel hydride modified with nano-nickel

    Science.gov (United States)

    Chen, Wei; Zhu, Yunfeng; Yang, Chen; Zhang, Jiguang; Li, Menghuai; Li, Liquan

    2015-04-01

    Magnesium nickel hydride (Mg2NiH4) used as negative electrode material in nickel-metal hydride (Ni-MH) secondary battery is modified by nano-nickel via mechanical milling. In this paper, we systematically investigate the microstructure and electrochemical properties of the modified system with different milling durations. X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) analyses confirm the amorphous transformation of Mg2Ni-based hydride and a novel NiH0.75 nanocrystalline with a diameter of about 5 nm embedding or covering on the surface of the base particle has been observed. Its formation mechanism and positive effects on electrochemical properties of the Mg2NiH4 have also been elaborated. Electrochemical measurements show that the 5 h milled composite possesses markedly increased discharge capacity up to 896 mAh g-1. With prolonging the milling duration from 5 h to 40 h, the discharge capacity at the 10th cycle increases from 99 mAh g-1 to 359 mAh g-1. Besides, the discharging procedure changes from stepwise processes to one single-step process with increasing the milling duration. Tafel polarization test shows that the nano-nickel modified system exhibits a much better anti-corrosion ability during charging/discharging cycles. Meanwhile, both the charge-transfer reaction on the alloy surface and hydrogen diffusion inside the alloy bulk are enhanced with nano-nickel modification.

  11. 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.

  12. Metal hydride work pair development and its application on automobile air conditioning systems

    Institute of Scientific and Technical Information of China (English)

    QIN Feng; CHEN Jiang-ping; ZHANG Wen-feng; CHEN Zhi-jiu

    2007-01-01

    Aiming at developing exhaust gas driving automobile air conditioning systems, a hydride pair LaNi4.61Mn0.26A10.13/La0.6Y0.4Ni4.8Mn0.2 was developed working at 393~473 K/293~323 K/263~273 K. Property tests showed that both alloys have flat plateau slopes and small hystereses; system theoretical coefficient of performance (COP) is 0.711. Based on this work pair, a function proving automobile metal hydride refrigeration system was constructed. The equivalent thermal conductivities of the activated reaction beds were merely 1.1~1.6 W/(m·K), which had not met practical requirement. Intermittent refrigeration cycles were achieved and the average cooling power was 84.6 W at 423 K/303 K/273 K with COP being 0.26. By altering cycling parameters, experiment data showed that cooling power and system COP increase with the growth of heat source temperature as well as pre-heating and regeneration time while decrease with heat sink temperature increment. This study confirms the feasibility of automobile metal hydride refrigeration systems, while heat transfer properties of reaction beds still need to be improved for better performance.

  13. Copper-Catalyzed Aerobic C–H Trifluoromethylation of Phenanthrolines

    Science.gov (United States)

    Zhu, Cheng-Liang; Zhang, Yong-Qiang; Yuan, Yong-An

    2016-01-01

    Direct C–H trifluoromethylation of heterocycles is a valuable transformation. In particular, nonprecious metal-catalyzed C–H trifluoromethylation processes, which do not proceed through CF3 radical species, have been less developed. In this cluster report, a new copper-catalyzed aerobic C–H trifluoromethylation of phenanthrolines is described. This transformation affords trifluoromethylated phenanthrolines that have not been synthesized and preliminary mechanistic studies suggest that the CF3 group transfer may occur through cooperative activation. PMID:26855477

  14. Enhanced hydrogen storage property of magnesium hydride by high surface area Raney nickel

    Energy Technology Data Exchange (ETDEWEB)

    Bhat, Vinay; Rougier, Aline; Aymard, Luc; Tarascon, Jean-Marie [University of Picardie, Amiens (France); Nazri, Gholam-Abbas [GMR and D, Chemical and Environmental Sciences Lab, Warren, MI (United States)

    2007-12-15

    This paper describes the improvement of hydrogen sorption capacity and kinetics of MgH{sub 2} by addition of high surface area ({approx}100m{sup 2}/g) Raney nickel (RN). Herein, we demonstrate that enhanced hydrogen sorption by MgH{sub 2} due to RN is not only linked to the catalytic nature of Ni, but also correlates well with the BET surface area for the MgH{sub 2}-Ni composites. The Raney Ni also tends to form the less stable Mg{sub 2}NiH{sub 4} hydrides, which desorb hydrogen at much higher pressure as compared with that of the MgH{sub 2}. We have observed a significant improvement in hydrogen sorption capacity and increase in pressure of hydrogen desorption for MgH{sub 2} catalyzed by RN. (author)

  15. Method of making crack-free zirconium hydride

    Science.gov (United States)

    Sullivan, Richard W.

    1980-01-01

    Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

  16. Creating nanoshell on the surface of titanium hydride bead

    Directory of Open Access Journals (Sweden)

    PAVLENKO Vyacheslav Ivanovich

    2016-12-01

    Full Text Available The article presents data on the modification of titanium hydride bead by creating titanium nanoshell on its surface by ion-plasma vacuum magnetron sputtering. To apply titanium nanoshell on the titanium hydride bead vacuum coating plant of multifunctional nanocomposite coatings QVADRA 500 located in the center of high technology was used. Analysis of the micrographs of the original surface of titanium hydride bead showed that the microstructure of the surface is flat, smooth, in addition the analysis of the microstructure of material surface showed the presence of small porosity, roughness, mainly cavities, as well as shallow longitudinal cracks. The presence of oxide film in titanium hydride prevents the free release of hydrogen and fills some micro-cracks on the surface. Differential thermal analysis of both samples was conducted to determine the thermal stability of the initial titanium hydride bead and bead with applied titanium nanoshell. Hydrogen thermal desorption spectra of the samples of the initial titanium hydride bead and bead with applied titanium nanoshell show different thermal stability of compared materials in the temperature range from 550 to 860о C. Titanium nanoshells applied in this way allows increasing the heat resistance of titanium hydride bead – the temperature of starting decomposition is 695о C and temperature when decomposition finishes is more than 1000о C. Modified in this way titanium hydride bead can be used as a filler in the radiation protective materials used in the construction or upgrading biological protection of nuclear power plants.

  17. Hydrogen storage in the form of metal hydrides

    Science.gov (United States)

    Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

    1984-01-01

    Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

  18. Electrochemical and Optical Properties of Magnesium-Alloy Hydrides Reviewed

    Directory of Open Access Journals (Sweden)

    Thirugnasambandam G. Manivasagam

    2012-10-01

    Full Text Available As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase hydrogen loading, provides precise control with only moderate reaction conditions. Interestingly, the alloy composition determines the crystallographic nature of the metal-hydride: a structural change is induced from rutile to fluorite at 80 at.% of Mg in Mg-TM alloy, with ensuing improved hydrogen mobility and storage capacity. So far, 6 wt.% (equivalent to 1600 mAh/g of reversibly stored hydrogen in MgyTM(1-yHx (TM: Sc, Ti has been reported. Thin film forms of these metal-hydrides reveal interesting electrochromic properties as a function of hydrogen content. Optical switching occurs during (dehydrogenation between the reflective metal and the transparent metal hydride states. The chronological sequence of the optical improvements in optically active metal hydrides starts with the rare earth systems (YHx, followed by Mg rare earth alloy hydrides (MgyGd(1-yHx and concludes with Mg transition metal hydrides (MgyTM(1-yHx. In-situ optical characterization of gradient thin films during (dehydrogenation, denoted as hydrogenography, enables the monitoring of alloy composition gradients simultaneously.

  19. High energy density battery based on complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  20. High energy density battery based on complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  1. Synthesis, characterization and properties of some organozinc hydride complexes

    NARCIS (Netherlands)

    Koning, A.J. de; Boersma, J.; Kerk, G.J.M. van der

    1980-01-01

    The synthesis and characterization of the monopyridine complexes of ethylzinc hydride and phenylzinc hydride are described. On treatment with TMED these complexes are converted into R2Zn3H4. TMED species through a combination of ligand-exchange and disproportionation. The formation of organozinc hyd

  2. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    Energy Technology Data Exchange (ETDEWEB)

    Shek, G.K. [Ontario Hydro Technol., Ont. (Canada). Mater. Technol. Unit; Jovanovic, M.T. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Seahra, H. [Ontario Hydro Technol., Ont. (Canada). Mater. Technol. Unit; Ma, Y. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Li, D. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Eadie, R.L. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extruded pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at K{sub I} below 12 MPa {radical}m at both 200 and 250 C very large striations (>40 {mu}m at 200 and >50 {mu}m at 250 C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when K{sub I} was increased beyond about 12 MPa {radical}m for these same specimens, the striation spacing decreased below 30 {mu}m, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface. (orig.).

  3. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    Science.gov (United States)

    Shek, G. K.; Jovanoviċ, M. T.; Seahra, H.; Ma, Y.; Li, D.; Eadie, R. L.

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extrude pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at KI below 12 MPa √m at both 200 and 250°C very large striations (> 40 μ at 200 and >50 μm at 250°C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when KI was increased beyond about 12 MPa √m for these same specimens, the striation spacing decreased below 30 μ, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface.

  4. High ramp rate thermogravimetric analysis of zirconium(II) hydride and titanium(II) hydride

    Energy Technology Data Exchange (ETDEWEB)

    Licavoli, Joseph J., E-mail: jjlicavo@mtu.edu; Sanders, Paul G., E-mail: sanders@mtu.edu

    2015-09-20

    Highlights: • A unique arc image device has been proposed for high ramp rate thermogravimetry. • Powder oxidation influences decomposition kinetics at temperatures below 933 K. • Particle size has a negligible effect on TiH{sub 2} decomposition behavior. • Improvements to the device are required to conduct accurate kinetic analysis. - Abstract: Zirconium and titanium hydride are utilized in liquid phase metal foam processing techniques. This application results in immediate exposure to molten metal and almost immediate decomposition at high temperatures. Most decomposition characterization techniques utilize slow heating rates and are unable to capture the decomposition behavior of hydrides under foam processing conditions. In order to address this issue a specialized high ramp rate thermogravimetric analyzer was created from a xenon arc image refiner. In addition to thermogravimetry, complimentary techniques including X-ray diffraction and scanning electron microscopy were used to characterize hydride decomposition and compare the results to literature. Hydrides were partially oxidized and separated into particles size ranges to evaluate the influence of these factors on decomposition. Oxidizing treatments were found to decrease decomposition rate only at temperatures below 933 K (660 °C) while particle size effects appeared to be negligible. Several improvements to the unique TGA apparatus presented in the current work are suggested to allow reliable kinetic modeling and analysis.

  5. Ni-, Pd-, or Pt-catalyzed ethylene dimerization: a mechanistic description of the catalytic cycle and the active species.

    Science.gov (United States)

    Roy, Dipankar; Sunoj, Raghavan B

    2010-03-07

    Two key mechanistic possibilities for group 10 transition metal [M(eta(3)-allyl)(PMe(3))](+) catalyzed (where M = Ni(II), Pd(II) and Pt(II)) ethylene dimerization are investigated using density functional theory methods. The nature of the potential active catalysts in these pathways is analyzed to gain improved insights into the mechanism of ethylene dimerization to butene. The catalytic cycle is identified as involving typical elementary steps in transition metal-catalyzed C-C bond formation reactions, such as oxidative insertion as well as beta-H elimination. The computed kinetic and thermodynamic features indicate that a commonly proposed metal hydride species (L(n)M-H) is less likely to act as the active species as compared to a metal-ethyl species (L(n)M-CH(2)CH(3)). Of the two key pathways considered, the active species is predicted to be a metal hydride in pathway-1, whereas a metal alkyl complex serves as the active catalyst in pathway-2. A metal-mediated hydride shift from a growing metal alkyl chain to the ethylene molecule, bound to the metal in an eta(2) fashion, is predicted to be the preferred route for the generation of the active species. Among the intermediates involved in the catalytic cycle, metal alkyls with a bound olefin are identified as thermodynamically stable for all three metal ions. In general, the Ni-catalyzed pathways are found to be energetically more favorable than those associated with Pd and Pt catalysts.

  6. Growth and decomposition of Lithium and Lithium hydride on Nickel

    DEFF Research Database (Denmark)

    Engbæk, Jakob; Nielsen, Gunver; Nielsen, Jane Hvolbæk

    2006-01-01

    In this paper we have investigated the deposition, structure and decomposition of lithium and lithium-hydride films on a nickel substrate. Using surface sensitive techniques it was possible to quantify the deposited Li amount, and to optimize the deposition procedure for synthesizing lithium......-hydride films. By only making thin films of LiH it is possible to study the stability of these hydride layers and compare it directly with the stability of pure Li without having any transport phenomena or adsorbed oxygen to obscure the results. The desorption of metallic lithium takes place at a lower...... temperature than the decomposition of the lithium-hydride, confirming the high stability and sintering problems of lithium-hydride making the storage potential a challenge. (c) 2006 Elsevier B.V. All rights reserved....

  7. Helium trapping at erbium oxide precipitates in erbium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Foiles, Stephen M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Battaile, Corbett Chandler [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-02-01

    The formation of He bubbles in erbium tritides is a significant process in the aging of these materials. Due to the long-standing uncertainty about the initial nucleation process of these bubbles, there is interest in mechanisms that can lead to the localization of He in erbium hydrides. Previous work has been unable to identify nucleation sites in homogeneous erbium hydride. This work builds on the experimental observation that erbium hydrides have nano- scale erbium oxide precipitates due to the high thermodynamic stability of erbium oxide and the ubiquitous presence of oxygen during materials processing. Fundamental DFT calculations indicate that the He is energetically favored in the oxide relative to the bulk hydride. Activation energies for the motion of He in the oxide and at the oxide-hydride interface indicate that trapping is kinetically feasible. A simple kinetic Monte Carlo model is developed that demonstrates the degree of trapping of He as a function of temperature and oxide fraction.

  8. Photochromism of rare-earth metal-oxy-hydrides

    Science.gov (United States)

    Nafezarefi, F.; Schreuders, H.; Dam, B.; Cornelius, S.

    2017-09-01

    Recently, thin films of yttrium oxy-hydride (YOxHy) were reported to show an unusual color-neutral photochromic effect promising for application in smart windows. Our present work demonstrates that also oxy-hydrides based on Gd, Dy, and Er have photochromic properties and crystal structures similar to YOxHy. Compared to YOxHy, the optical bandgaps of the lanthanide based oxy-hydrides are smaller while photochromic contrast and kinetics show large variation among different cations. Based on these findings, we propose that cation alloying is a viable pathway to tailor the photochromic properties of oxy-hydride materials. Furthermore, we predict that the oxy-hydrides of the other lanthanides are also potentially photochromic.

  9. Metal hydrides for concentrating solar thermal power energy storage

    Science.gov (United States)

    Sheppard, D. A.; Paskevicius, M.; Humphries, T. D.; Felderhoff, M.; Capurso, G.; Bellosta von Colbe, J.; Dornheim, M.; Klassen, T.; Ward, P. A.; Teprovich, J. A.; Corgnale, C.; Zidan, R.; Grant, D. M.; Buckley, C. E.

    2016-04-01

    The development of alternative methods for thermal energy storage is important for improving the efficiency and decreasing the cost of concentrating solar thermal power. We focus on the underlying technology that allows metal hydrides to function as thermal energy storage (TES) systems and highlight the current state-of-the-art materials that can operate at temperatures as low as room temperature and as high as 1100 °C. The potential of metal hydrides for thermal storage is explored, while current knowledge gaps about hydride properties, such as hydride thermodynamics, intrinsic kinetics and cyclic stability, are identified. The engineering challenges associated with utilising metal hydrides for high-temperature TES are also addressed.

  10. Results of NDE Technique Evaluation of Clad Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kunerth, Dennis C. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-09-01

    This report fulfills the M4 milestone, M4FT-14IN0805023, Results of NDE Technique Evaluation of Clad Hydrides, under Work Package Number FT-14IN080502. During service, zirconium alloy fuel cladding will degrade via corrosion/oxidation. Hydrogen, a byproduct of the oxidation process, will be absorbed into the cladding and eventually form hydrides due to low hydrogen solubility limits. The hydride phase is detrimental to the mechanical properties of the cladding and therefore it is important to be able to detect and characterize the presence of this constituent within the cladding. Presently, hydrides are evaluated using destructive examination. If nondestructive evaluation techniques can be used to detect and characterize the hydrides, the potential exists to significantly increase test sample coverage while reducing evaluation time and cost. To demonstrate the viability this approach, an initial evaluation of eddy current and ultrasonic techniques were performed to demonstrate the basic ability to these techniques to detect hydrides or their effects on the microstructure. Conventional continuous wave eddy current techniques were applied to zirconium based cladding test samples thermally processed with hydrogen gas to promote the absorption of hydrogen and subsequent formation of hydrides. The results of the evaluation demonstrate that eddy current inspection approaches have the potential to detect both the physical damage induced by hydrides, e.g. blisters and cracking, as well as the combined effects of absorbed hydrogen and hydride precipitates on the electrical properties of the zirconium alloy. Similarly, measurements of ultrasonic wave velocities indicate changes in the elastic properties resulting from the combined effects of absorbed hydrogen and hydride precipitates as well as changes in geometry in regions of severe degradation. However, for both approaches, the signal responses intended to make the desired measurement incorporate a number of contributing

  11. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    Science.gov (United States)

    Rico, A.; Martin-Rengel, M. A.; Ruiz-Hervias, J.; Rodriguez, J.; Gomez-Sanchez, F. J.

    2014-09-01

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young's modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young's modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found.

  12. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    Energy Technology Data Exchange (ETDEWEB)

    Rico, A., E-mail: alvaro.rico@urjc.es [DIMME, Departamento de Tecnología Mecánica, Universidad Rey Juan Carlos, c/Tulipán s/n, E-28933 Móstoles, Madrid (Spain); Martin-Rengel, M.A., E-mail: mamartin@mater.upm.es [Departamento de Ciencia de los Materiales, UPM, E.T.S.I. Caminos, Canales y Puertos, Profesor Aranguren SN, E-28040 Madrid (Spain); Ruiz-Hervias, J., E-mail: jesus.ruiz@upm.es [Departamento de Ciencia de los Materiales, UPM, E.T.S.I. Caminos, Canales y Puertos, Profesor Aranguren SN, E-28040 Madrid (Spain); Rodriguez, J. [DIMME, Departamento de Tecnología Mecánica, Universidad Rey Juan Carlos, c/Tulipán s/n, E-28933 Móstoles, Madrid (Spain); Gomez-Sanchez, F.J., E-mail: javier.gomez@amsimulation.com [Advanced Material Simulation, S.L, Madrid (Spain)

    2014-09-15

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young’s modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young’s modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found.

  13. Study on Kinetics of Hydrogen Absorption by Metal Hydride Slurries Ⅰ. Absorption of Hydrogen by Hydrogen Storage Alloy MlNi5 Suspended in Benzene

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

    The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three-phase mass transfer model. It is also concluded that the suitable absorption temperature is 313 K.

  14. Nanostructured Magnesium Hydride for Reversible Hydrogen Storage

    Science.gov (United States)

    de Rango, P.; Chaise, A.; Fruchart, D.; Miraglia, S.; Marty, Ph.

    2013-05-01

    The aim of this work was to develop suitable materials to store hydrogen in a solid state. A systematic investigation of the co-milling process of magnesium hydride with a transition metal was undertaken in order to produce nanostructured and highly reactive powders. The initiating role of the transition metal was evidenced by in situ neutron diffraction experiments. High performances in terms of thermal and mechanical behavior were achieved introducing expanded graphite and compacting the mixture to form composite materials. Absorption and desorption kinetics have been measured versus temperature and H2 pressure.

  15. Lithium hydride - A space age shielding material

    Science.gov (United States)

    Welch, F. H.

    1974-01-01

    Men and materials performing in the environment of an operating nuclear reactor require shielding from the escaping neutron particles and gamma rays. For efficient shielding from gamma rays, dense, high atomic number elements such as iron, lead, or tungsten are required, whereas light, low atomic number elements such as hydrogen, lithium, or beryllium are required for efficient neutron shielding. The use of lithium hydride (LiH) as a highly efficient neutron-shielding material is considered. It contains, combined into a single, stable compound, two of the elements most effective in attenuating and absorbing neutrons.

  16. Highly Concentrated Palladium Hydrides/Deuterides; Theory

    Energy Technology Data Exchange (ETDEWEB)

    Papaconstantopoulos, Dimitrios

    2013-11-26

    Accomplishments are reported in these areas: tight-binding molecular dynamics study of palladium; First-principles calculations and tight-binding molecular dynamics simulations of the palladium-hydrogen system; tight-binding studies of bulk properties and hydrogen vacancies in KBH{sub 4}; tight-binding study of boron structures; development of angular dependent potentials for Pd-H; and density functional and tight-binding calculations for the light-hydrides NaAlH4 and NaBH4

  17. Development of nickel-metal hydride cell

    Science.gov (United States)

    Kuwajima, Saburo; Kamimori, Nolimits; Nakatani, Kensuke; Yano, Yoshiaki

    1993-01-01

    National Space Development Agency of Japan (NASDA) has conducted the research and development (R&D) of battery cells for space use. A new R&D program about a Nickel-Metal Hydride (Ni-MH) cell for space use from this year, based on good results in evaluations of commercial Ni-MH cells in Tsukuba Space Center (TKSC), was started. The results of those commercial Ni-MH cell's evaluations and recent status about the development of Ni-MH cells for space use are described.

  18. Materials considerations in the design of a metal-hydride heat pump for an advanced extravehicular mobility unit

    Science.gov (United States)

    Liebert, B. E.

    1986-01-01

    A metal-hydride heat pump (HHP) has been proposed to provide an advanced regenerable nonventing thermal sink for the liquid-cooled garment worn during an extravehicular activity (EVA). The conceptual design indicates that there is a potential for significant advantages over the one presently being used by shuttle crew personnel as well as those that have been proposed for future use with the space station. Compared to other heat pump designs, a HHP offers the potential for extended use with no electrical power requirements during the EVA. In addition, a reliable, compact design is possible due to the absence of moving parts other than high-reliability check valves. Because there are many subtleties in the properties of metal hydrides for heat pump applications, it is essential that a prototype hydride heat pump be constructed with the selected materials before a committment is made for the final design. Particular care must be given to the evaporator heat exchanger worn by the astronaut since the performance of hydride heat pumps is generally heat transfer limited.

  19. The mechanism for iron-catalyzed alkene isomerization in solution

    Energy Technology Data Exchange (ETDEWEB)

    Sawyer, Karma R.; Glascoe, Elizabeth A.; Cahoon, James F.; Schlegel, Jacob P.; Harris, Charles B.

    2008-05-27

    Here we report nano- through microsecond time-resolved IR experiments of iron-catalyzed alkene isomerization in room-temperature solution. We have monitored the photochemistry of a model system, Fe(CO){sub 4}({eta}{sup 2}-1-hexene), in neat 1-hexene solution. UV-photolysis of the starting material leads to the dissociation of a single CO to form Fe(CO){sub 3}({eta}{sup 2}-1-hexene), in a singlet spin state. This CO loss complex shows a dramatic selectivity to form an allyl hydride, HFe(CO){sub 3}({eta}{sup 3}-C{sub 6}H{sub 11}), via an internal C-H bond-cleavage reaction in 5-25 ns. We find no evidence for the coordination of an alkene molecule from the bath to the CO loss complex, but do observe coordination to the allyl hydride, indicating that it is the key intermediate in the isomerization mechanism. Coordination of the alkene ligand to the allyl hydride leads to the formation of the bis-alkene isomers, Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) and Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2}. Because of the thermodynamic stability of Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) over Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2} (ca. 12 kcal/mol), nearly 100% of the alkene population will be 2-alkene. The results presented herein provide the first direct evidence for this mechanism in solution and suggest modifications to the currently accepted mechanism.

  20. Effect of design parameters on enhancement of hydrogen charging in metal hydride reactors

    Energy Technology Data Exchange (ETDEWEB)

    Kaplan, Y. [Mechanical Engineering Department, Nigde University, 51100 Nigde (Turkey)

    2009-03-15

    The effects of heat transfer mechanisms on the charging process in metal hydride reactors are studied under various charging pressures. Three different cylindrical reactors with the same base dimensions are designed and manufactured. The first one is a closed cylinder cooled with natural convection, the fins are manufactured around the second reactor and the third reactor is cooled with water circulating around the reactor. The temperatures of the reactor at several locations are measured during charging with a range of pressure of 1-10 bar. The third reactor shows the lowest temperature increase with the fastest charging time under all charging pressures investigated. The effective heat transfer coefficients of the reactors are also calculated according to the experimental results and they are found to be 5.5 {+-} 1 W m{sup -2} K{sup -1}, 35 {+-} 2 W m{sup -2} K{sup -1} and 113 {+-} 1 W m{sup -2} K{sup -1}, respectively. The experimental results showed that the charging of hydride reactors is mainly heat transfer dependent and the reactor with better cooling exhibits the fastest charging characteristics. (author)

  1. NATO Advanced Study Institute on Metal Hydrides

    CERN Document Server

    1981-01-01

    In the last five years, the study of metal hydrides has ex­ panded enormously due to the potential technological importance of this class of materials in hydrogen based energy conversion schemes. The scope of this activity has been worldwide among the industrially advanced nations. There has been a consensus among researchers in both fundamental and applied areas that a more basic understanding of the properties of metal/hydrogen syster;,s is required in order to provide a rational basis for the selection of materials for specific applications. The current worldwide need for and interest in research in metal hydrides indicated the timeliness of an Advanced Study Insti­ tute to provide an in-depth view of the field for those active in its various aspects. The inclusion of speakers from non-NATO coun­ tries provided the opportunity for cross-fertilization of ideas for future research. While the emphasis of the Institute was on basic properties, there was a conscious effort to stimulate interest in the applic...

  2. From permanent magnets to rechargeable hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Willems, J.J.G.; Buschow, K.H.J.

    1987-02-15

    A brief historical survey is given of how the study of coercitivity mechanisms in SmCo/sub 5/ permanent-magnet materials eventually led to the discovery of the favourable hydrogen sorption properties of the compound LaNi/sub 5/. It is shown how continued research by many investigators dealing with a variety of different physical and chemical properties has resulted in an advanced understanding of some of the principles that govern hydrogen absorption and which are responsible for the changes in physical properties that accompany it. The problems associated with various applications of LaNi/sub 5/-based hydrogen-storage materials are also briefly discussed. A large part of this paper is devoted to the applicability of LaNi/sub 5/-type materials in batteries. Research in this area has resulted in the development of a new type of rechargeable battery: the nickel-hydride cell. This battery can be charged and discharged at high rates and is relatively insensitive to overcharging and overdischarging. Special attention is given to the nature of the electrode degradation process and the effect of composition variations in LaNi/sub 5/-related materials on the lifetime of the corresponding hydride electrodes when subjected to severe electrochemical charge-discharge cycles.

  3. Metal hydrides for lithium-ion batteries.

    Science.gov (United States)

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries.

  4. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    Science.gov (United States)

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-02

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

  5. Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides.

    Science.gov (United States)

    Belkova, Natalia V; Epstein, Lina M; Filippov, Oleg A; Shubina, Elena S

    2016-08-10

    The dihydrogen bond-an interaction between a transition-metal or main-group hydride (M-H) and a protic hydrogen moiety (H-X)-is arguably the most intriguing type of hydrogen bond. It was discovered in the mid-1990s and has been intensively explored since then. Herein, we collate up-to-date experimental and computational studies of the structural, energetic, and spectroscopic parameters and natures of dihydrogen-bonded complexes of the form M-H···H-X, as such species are now known for a wide variety of hydrido compounds. Being a weak interaction, dihydrogen bonding entails the lengthening of the participating bonds as well as their polarization (repolarization) as a result of electron density redistribution. Thus, the formation of a dihydrogen bond allows for the activation of both the MH and XH bonds in one step, facilitating proton transfer and preparing these bonds for further transformations. The implications of dihydrogen bonding in different stoichiometric and catalytic reactions, such as hydrogen exchange, alcoholysis and aminolysis, hydrogen evolution, hydrogenation, and dehydrogenation, are discussed.

  6. Filiform-mode hydride corrosion of uranium surfaces

    Science.gov (United States)

    Hill, M. A.; Schulze, R. K.; Bingert, J. F.; Field, R. D.; McCabe, R. J.; Papin, P. A.

    2013-11-01

    Hydride nucleation and growth has previously been studied in uranium with an air-formed oxide. Preferred directional growth of uranium hydride has not been observed, presumably due to the constraint of the oxide layer and/or the presence of a surface layer distorted by mechanical grinding and polishing. Instead, hydrides typically first form as subsurface blisters that do not exhibit preferred growth directionality. By eliminating the strained surface layer through electropolishing, removing the natural oxide through ion sputtering, avoiding exposure of the uranium to air, and then exposing uranium to high purity hydrogen in an environmental cell, hydride growth patterns emerge that correspond to defect structures within the microstructure. These hydride growth patterns are similar to filiform corrosion, a type of corrosion that frequently forms under thin protective films. This work describes the first reported observation of filiform-like corrosion in uranium. The uranium hydride initiates at defects, but grows into filaments up to 20 μm wide, and tends to form in straight lines, largely propagating along twin boundaries. Propagation is driven by hydrogen reaction at the filament head, promoted by more efficient delivery of reactant. However, this phenomenon does not involve an electrochemical process associated with conventional filiform corrosion and is therefore described as filiform-like. Hydride growth was observed using optical microscopy for a period of nearly three years. Sample characterization included automated electron backscatter diffraction (EBSD) measurements to determine growth directions. Observation of this anomalous hydride growth provides clues as to the mechanisms operating in uranium hydriding for more conventionally prepared sample surfaces.

  7. Technical and economic aspects of hydrogen storage in metal hydrides

    Science.gov (United States)

    Schmitt, R.

    1981-01-01

    The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

  8. PIE techniques for hydride reorientation test at NDC

    Energy Technology Data Exchange (ETDEWEB)

    Tsuda, Tomohiro; Shinohara, Yasunari; Yamaguchi, Yoichiro [Nuclear Development Corporation, Ibaraki (Japan)

    2008-11-15

    Dry storage of spent fuels in the interim storage facility is being planned in Japan. However, the gradual deterioration of the mechanical property of fuel cladding due to internal pressure and temperature during the storage term is known. Therefore, the integrity of stored fuel rods should be confirmed before the start of dry storage. For the last several years, NDC had a lot of experiences on the hydride reorientation test. The specimen preparation techniques on the hydride reorientation test and the mechanical testing techniques after the hydride reorientation are shown in this paper.

  9. Effect of lanthanum hydride on microstructures and hydrogen storage performances of 2LiNH2-MgH2 system

    Institute of Scientific and Technical Information of China (English)

    朱惜林; 韩树民; 赵鑫; 李媛; 刘宝忠

    2014-01-01

    Hydrogen storage properties of 2LiNH2-MgH2 system were improved by adding lanthanum hydride (LaH3), and the role of LaH3 in hydrogen sorption process of Li-Mg-N-H system was investigated. Temperature programmed sorption results showed that the addition of lanthanum hydride reduced the dehydriding/hydriding onset temperature of 2LiNH2-MgH2 system by at least 15 K. Moreover, A 0.053 wt.%/min average rate was determined for the hydrogen desorption of 2LiNH2-MgH2-0.05LaH3 composite, while it was only 0.035 wt.%/min for 2LiNH2-MgH2 system. Hydrogen absorption capacity increased from 1.62 wt.% to 2.12 wt.% within 200 min by adding LaH3 into 2LiNH2-MgH2 system at 383 K. In the dehydrogenation of 2LiNH2-MgH2-0.05LaH3 composite, LaH2 transferred to LaN phase, which reversed to LaH2 in the following hydrogen adsorption process. The reversible reaction of LaH2 ef-fectively promoted the hydrogen sorption of Li-Mg-N-H system. Moreover, the homogenous distribution of fine La hydride was fa-vorable to improving effect of lanthanum hydride.

  10. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  11. Technical and economic evaluation of hydrogen storage systems based on light metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jepsen, Julian

    2014-07-01

    Novel developments regarding materials for solid-state hydrogen storage show promising prospects. These complex hydrides exhibit high mass-related storage capacities and thus great technical potential to store hydrogen in an efficient and safe way. However, a comprehensive evaluation of economic competitiveness is still lacking, especially in the case of the LiBH4 / MgH2 storage material. In this study, an assessment with respect to the economic feasibility of implementing complex hydrides as hydrogen storage materials is presented. The cost structure of hydrogen storage systems based on NaAlH4 and LiBH4 / MgH2 is discussed and compared with the conventional high pressure (700 bar) and liquid storage systems. Furthermore, the properties of LiBH4 / MgH2, so-called Li-RHC (Reactive Hydride Composite), are scientifically compared and evaluated on the lab and pilot plant scale. To enhance the reaction rate, the addition of TiCl3 is investigated and high energy ball milling is evaluated as processing technique. The effect of the additive in combination with the processing technique is described in detail. Finally, an optimum set of processing parameters and additive content are identified and can be applied for scaled-up production of the material based on simple models considering energy input during processing. Furthermore, thermodynamic, heat transfer and kinetic properties are experimentally determined by different techniques and analysed as a basis for modelling and designing scaled-up storage systems. The results are analysed and discussed with respect to the reaction mechanisms and reversibility of the system. Heat transfer properties are assessed with respect to the scale-up for larger hydrogen storage systems. Further improvements of the heat transfer were achieved by compacting the material. In this regard, the influence of the compaction pressure on the apparent density, thermal conductivity and sorption behaviour, was investigated in detail. Finally, scaled

  12. Merging Visible Light Photoredox Catalysis with Metal Catalyzed C–H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants

    Science.gov (United States)

    2016-01-01

    catalyst via a coupled electron transfer (ET) process. Here we describe our first successful endeavors to address the above challenges by combining visible light photoredox catalysis with different ruthenium, rhodium, or palladium catalyzed C–H activations. Since only small amounts of the oxidant are generated and are immediately consumed in these transformations, side reactions of substrates or products can be avoided. Thus, usually oxidant-sensible substrates can be used, which makes these methods highly suitable for complex molecular structure syntheses. Moreover, mechanistic studies shed light on new reaction pathways, intermediates, and in situ generated species. The successful development of our dual catalysis concept, consisting of combined visible light photoredox catalysis and metal catalyzed C–H functionalization, provides many new opportunities for further explorations in the field of C–H functionalization. PMID:27556812

  13. Successive heterolytic cleavages of H2 achieve N2 splitting on silica-supported tantalum hydrides: A DFT proposed mechanism

    KAUST Repository

    Soláns, Xavier Luis

    2012-07-02

    DFT(B3PW91) calculations have been carried out to propose a pathway for the N2 cleavage by H2 in the presence of silica-supported tantalum hydride complexes [(≡ SiO)2TaHx] that forms [(≡SiO)2Ta(NH)(NH2)] (Science2007, 317, 1056). The calculations, performed on the cluster models {μ-O[(HO)2SiO] 2}TaH1 and {μ-O[(HO)2SiO] 2}TaH3, labelled as (≡SiO)2TaH x (x = 1, 3), show that the direct hydride transfers to coordinated N-based ligands in (≡SiO)2TaH(η2-N2) and (≡SiO)2TaH(η2-HNNH) have high energy barrier barriers. These high energy barriers are due in part to a lack of energetically accessible empty orbitals in the negatively charged N-based ligands. It is shown that a succession of proton transfers and reduction steps (hydride transfer or 2 electron reduction by way of dihydride reductive coupling) to the nitrogen-based ligands leads to more energetically accessible pathways. These proton transfers, which occur by way of heterolytic activation of H2, increase the electrophilicity of the resulting ligand (diazenido, N 2H-, and hydrazido, NHNH2-, respectively) that can thus accept a hydride with a moderate energy barrier. In the case of (≡SiO)2TaH(η2-HNNH), the H 2 molecule that is adding across the Ta-N bond is released after the hydride transfer step by heterolytic elimination from (≡SiO) 2TaH(NH2)2, suggesting that dihydrogen has a key role in assisting the final steps of the reaction without itself being consumed in the process. This partly accounts for the experimental observation that the addition of H2 is needed to convert an intermediate, identified as a diazenido complex [(≡SiO)2TaH(η 2-HNNH)] from its ν(N-H) stretching frequency of 3400 cm -1, to the final product. Throughout the proposed mechanism, the tantalum remains in its preferred high oxidation state and avoids redox-type reactions, which are more energetically demanding. © 2012 American Chemical Society.

  14. Acute arsenious hydride intoxication. Four cases

    Energy Technology Data Exchange (ETDEWEB)

    Gosselin, B.; Mathieu, D.; Desprez-Nolf, M.; Cosson, A.; Goudemand, J.; Haguenoer, J.M.; Wattel, F.

    1982-02-06

    While engaged in the repair of a zinc furnace, 4 workers were accidentally exposed to arsenious hydride (AsH3) fumes. Acute intravascular haemolysis developed within a few hours. On admission, the patients immediately underwent exsanguino-transfusion; 8.2 to 10.2 l of blood were exchanged through a continuous perfusion pump at the rate of 1 l/hour. Two patients resumed diuresis during transfusion, but the other two required repeated haemodialysis. Between the 10th and 30th days, while renal function was gradually returning to normal, mildly megaloblastic anaemia developed. This was followed during the 3rd month by clinical and electric signs of polyneuritis of the lower and upper limbs, which subsequently regressed. Regular measurements of arsenic levels in the blood and urine were performed between and during exsanguino-transfusion and haemodialysis.

  15. Hydrogen desorption from nanostructured magnesium hydride composites

    Directory of Open Access Journals (Sweden)

    Brdarić Tanja P.

    2007-01-01

    Full Text Available The influence of 3d transition metal addition (Fe, Co and Ni on the desorption properties of magnesium hydride were studied. The ball milling of MgH2-3d metal blends was performed under Ar. Microstructural and morphological characterization were performed by XRD and SEM analysis, while the hydrogen desorption properties were investigated by DSC. The results show a strong correlation between the morphology and thermal stability of the composites. The complex desorption behavior (the existence of more than one desorption peak was correlated with the dispersion of the metal additive particles that appear to play the main role in the desorption. The desorption temperature can be reduced by more than 100 degrees if Fe is added as additive. The activation energy for H2 desorption from the MgH2-Fe composite is 120 kJ/mol, implying that diffusion controls the dehydration process.

  16. Review of magnesium hydride-based materials: development and optimisation

    NARCIS (Netherlands)

    Crivello, J. -C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.|info:eu-repo/dai/nl/186125372; Latroche, M.; Milanese, C.; Milcius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the

  17. Direct observation of hydrides formation in cavity-grade niobium

    Directory of Open Access Journals (Sweden)

    F. Barkov

    2012-12-01

    Full Text Available Niobium is an important technological superconductor used to make radio frequency cavities for particle accelerators. Using laser confocal microscopy we have directly investigated hydride precipitates formation in cavity-grade niobium at 77 and 140 K. We have found that large hydrides were usually formed after chemical or mechanical treatments, which are known to lead to a strong degradation of the quality factor known as Q disease. From our experiments we can conclude that hydrides causing Q disease are islands with a characteristic thickness of ≳100  nm and in-plane dimensions 1–10  μm. Our results show that mechanical polishing uploads a lot of hydrogen into bulk niobium while electropolishing leads to a mild contamination. Vacuum treatments at 600–800°C are demonstrated to preclude large hydride formation in line with the absence of Q disease in similarly treated cavities.

  18. Materials science of Mg-Ni-based new hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Orimo, S.; Fujii, H. [Hiroshima Univ. (Japan). Faculty of Integrated Arts and Sciences

    2001-02-01

    One of the advantageous functional properties of Mg alloys (or compounds) is to exhibit the reversible hydriding reaction. In this paper, we present our systematic studies regarding the relationship between nanometer- or atomistic-scale structures and the specific hydriding properties of the Mg-Ni binary system, such as(1) nanostructured (n)-Mg{sub 2}Ni, (2) a mixture of n-Mg{sub 2}Ni and amorphous (a)-MgNi,(3) pure a-MgNi, and(4) n-MgNi{sub 2}. Further studies on(5) an a-MgNi-based system for clarifying the effect of the short-range ordering on the structural and hydriding properties and(6) a MgNi{sub 2}-based system for synthesizing the new Laves phase structure are also presented. The materials science of Mg-Ni-based new hydrides will provide indispensable knowledge for practically developing the Mg alloys as hydrogen-storage materials. (orig.)

  19. Structure and bonding of second-row hydrides

    OpenAIRE

    Blinder, S. M.

    2014-01-01

    The atomic orbitals, hybridization and chemical bonding of the most common hydrides of boron, carbon, nitrogen and oxygen are described. This can be very instructive for beginning students in chemistry and chemical physics.

  20. DETERMINATION OF METAL HYDRIDE SYSTEMS CHARACTERISTICS WHILE HEATING

    Directory of Open Access Journals (Sweden)

    Yu. Kluchka

    2012-01-01

    Full Text Available Experimental dependence of the pressure of hydrogen in the hydride cartridge when it is heated is obtained. Experimental data prove the theoretical values with an accuracy of ≈ 6%.

  1. Bipolar Nickel-Metal Hydride Battery Being Developed

    Science.gov (United States)

    Manzo, Michelle A.

    1998-01-01

    The NASA Lewis Research Center has contracted with Electro Energy, Inc., to develop a bipolar nickel-metal hydride battery design for energy storage on low-Earth-orbit satellites. The objective of the bipolar nickel-metal hydride battery development program is to approach advanced battery development from a systems level while incorporating technology advances from the lightweight nickel electrode field, hydride development, and design developments from nickel-hydrogen systems. This will result in a low-volume, simplified, less-expensive battery system that is ideal for small spacecraft applications. The goals of the program are to develop a 1-kilowatt, 28-volt (V), bipolar nickel-metal hydride battery with a specific energy of 100 watt-hours per kilogram (W-hr/kg), an energy density of 250 W-hr/liter and a 5-year life in low Earth orbit at 40-percent depth-of-discharge.

  2. High-pressure synthesis of noble metal hydrides.

    Science.gov (United States)

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-07

    The formation of hydride phases in the noble metals copper, silver, and gold was investigated by in situ x-ray diffraction at high hydrogen pressures. In the case of copper, a novel hexagonal hydride phase, Cu2H, was synthesised at pressures above 18.6 GPa. This compound exhibits an anti-CdI2-type structure, where hydrogen atoms occupy every second layer of octahedral interstitial sites. In contrast to chemically produced CuH, this phase does not show a change in compressibility compared to pure copper. Furthermore, repeated compression (after decomposition of Cu2H) led to the formation of cubic copper hydride at 12.5 GPa, a phenomenon attributed to an alteration of the microstructure during dehydrogenation. No hydrides of silver (up to 87 GPa) or gold (up to 113 GPa) were found at both room and high temperatures.

  3. Out-of-pile accelerated hydriding of Zircaloy fasteners

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, J.C.

    1979-10-01

    Mechanical joints between Zircaloy and nickel-bearing alloys, mainly the Zircaloy-4/Inconel-600 combination, were exposed to water at 450/sup 0/F and 520/sup 0/F to study hydriding of Zircaloy in contact with a dissimilar metal. Accelerated hydriding of the Zircaloy occurred at both temperatures. At 450/sup 0/F the dissolved hydrogen level of the water was over ten times that at 520/sup 0/F. At 520/sup 0/F the initially high hydrogen ingress rate decreased rapidly as exposure time increased and was effectively shut off in about 25 days. Severely hydrided Zircaloy components successfully withstood thermal cycling and mechanical testing. Chromium plating of the nickel-bearing parts was found to be an effective and practical barrier in preventing nickel-alloy smearing and accelerated hydriding of Zircaloy.

  4. Hydrogen storage in sodium aluminum hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Ozolins, Vidvuds; Herberg, J.L. (Lawrence Livermore National Laboratories, Livermore, CA); McCarty, Kevin F.; Maxwell, Robert S. (Lawrence Livermore National Laboratories, Livermore, CA); Stumpf, Roland Rudolph; Majzoub, Eric H.

    2005-11-01

    Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.

  5. Electronic structure of ternary hydrides based on light elements

    Energy Technology Data Exchange (ETDEWEB)

    Orgaz, E. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)]. E-mail: orgaz@eros.pquim.unam.mx; Membrillo, A. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Castaneda, R. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Aburto, A. [Departamento de Fisica, Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)

    2005-12-08

    Ternary hydrides based on light elements are interesting owing to the high available energy density. In this work we focused into the electronic structure of a series of known systems having the general formula AMH{sub 4}(A=Li,Na,M=B,Al). We computed the energy bands and the total and partial density of states using the linear-augmented plane waves method. In this report, we discuss the chemical bonding in this series of complex hydrides.

  6. Ab-Initio Study of the Group 2 Hydride Anions

    Science.gov (United States)

    Harris, Joe P.; Wright, Timothy G.; Manship, Daniel R.

    2013-06-01

    The beryllium hydride (BeH)- dimer has recently been shown to be surprisingly strongly bound, with an electronic structure which is highly dependent on internuclear separation. At the equilibrium distance, the negative charge is to be found on the beryllium atom, despite the higher electronegativity of the hydrogen. The current study expands this investigation to the other Group 2 hydrides, and attempts to explain these effects. M. Verdicchio, G. L. Bendazzoli, S. Evangelisti, T. Leininger J. Phys. Chem. A, 117, 192, (2013)

  7. Suppression of the critical temperature in binary vanadium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Dolan, M.D., E-mail: michael.dolan@csiro.au [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); McLennan, K.G. [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); Chandra, D. [Department of Chemical and Materials Engineering, University of Nevada, Reno, Reno, NV 89557 (United States); Kochanek, M.A. [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); Song, G. [CSIRO Process Science and Engineering, Gate 4, Normanby Rd, Clayton, VIC 3168 (Australia)

    2014-02-15

    Highlights: • Addition of 10 mol% Cr to V increases the β-hydride T{sub C} to >200 °C. • Addition of 10 mol% Ni to V increases the β-hydride T{sub C} to >400 °C. • Addition of 10 mol% Al to V decreases the β-hydride T{sub C} to <30 °C. • V{sub 90}Al{sub 10} membrane can be cycled to <30 °C under H{sub 2} without β-hydride formation. -- Abstract: The tendency of vanadium-based alloy membranes to embrittle is the biggest commercialisation barrier for this hydrogen separation technology. Excessive hydrogen absorption and the α → β hydride transition both contribute to brittle failure of these membranes. Alloying is known to reduce absorption, but the influence of alloying on hydride phase formation under conditions relevant to membrane operation has not been studied in great detail previously. Here, the effect of Cr, Ni, and Al alloying additions on V–H phase equilibrium has been studied using hydrogen absorption measurements and in situ X-ray diffraction studies. The addition of 10 mol% Ni increases the critical temperature for α + β hydride formation to greater than 400 °C, compared to 170 °C for V. Cr also increases the critical temperature, to between 200 and 300 °C. The addition of 10 mol% Al, however, suppresses the critical temperature to less than 30 °C, thereby enabling this material to be cycled thermally and hydrostatically while precluding formation of the β-hydride phase. This is despite Al also decreasing hydrogen absorption. The implication of this finding is that one of the mechanisms of brittle failure in vanadium-based hydrogen-selective membranes has been eliminated, thereby increasing the robustness of this material relative to V.

  8. Method of selective reduction of polyhalosilanes with alkyltin hydrides

    Science.gov (United States)

    Sharp, Kenneth G.; D'Errico, John J.

    1989-01-01

    The invention relates to the selective and stepwise reduction of polyhalosilanes by reacting at room temperature or below with alkyltin hydrides without the use of free radical intermediates. Alkyltin hydrides selectively and stepwise reduce the Si--Br, Si--Cl, or Si--I bonds while leaving intact any Si--F bonds. When two or more different halogens are present on the polyhalosilane, the halogen with the highest atomic weight is preferentially reduced.

  9. Method of selective reduction of halodisilanes with alkyltin hydrides

    Science.gov (United States)

    D'Errico, John J.; Sharp, Kenneth G.

    1989-01-01

    The invention relates to the selective and sequential reduction of halodisilanes by reacting these compounds at room temperature or below with trialkyltin hydrides or dialkyltin dihydrides without the use of free radical intermediates. The alkyltin hydrides selectively and sequentially reduce the Si-Cl, Si-Br or Si-I bonds while leaving intact the Si-Si and Si-F bonds present.

  10. Electronic structure and optical properties of lightweight metal hydrides

    NARCIS (Netherlands)

    Setten, van M.J.; Popa, V.A.; Wijs, de G.A.; Brocks, G.

    2007-01-01

    We study the dielectric functions of the series of simple hydrides LiH, NaH, MgH2, and AlH3, and of the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4, and Mg(AlH4)2, using first-principles density-functional theory and GW calculations. All compounds are large gap insulators with GW single-partic

  11. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.

    2012-06-29

    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  12. Optimization of Hydride Rim Formation in Unirradiated Zr 4 Cladding

    Energy Technology Data Exchange (ETDEWEB)

    Shimskey, Rick W.; Hanson, Brady D.; MacFarlan, Paul J.

    2013-09-30

    The purpose of this work is to build on the results reported in the M2 milestone M2FT 13PN0805051, document number FCRD-USED-2013-000151 (Hanson, 2013). In that work, it was demonstrated that unirradiated samples of zircaloy-4 cladding could be pre-hydrided at temperatures below 400°C in pure hydrogen gas and that the growth of hydrides on the surface could be controlled by changing the surface condition of the samples and form a desired hydride rim on the outside diameter of the cladding. The work performed at Pacific Northwest National Laboratory since the issuing of the M2 milestone has focused its efforts to optimize the formation of a hydride rim on available zircaloy-4 cladding samples by controlling temperature variation and gas flow control during pre-hydriding treatments. Surface conditioning of the outside surface was also examined as a variable. The results of test indicate that much of the variability in the hydride thickness is due to temperature variation occurring in the furnaces as well as how hydrogen gas flows across the sample surface. Efforts to examine other alloys, gas concentrations, and different surface conditioning plan to be pursed in the next FY as more cladding samples become available

  13. Mechanochemical synthesis of nanostructured chemical hydrides in hydrogen alloying mills

    Energy Technology Data Exchange (ETDEWEB)

    Wronski, Z. [CANMET' s Materials Technology Laboratory, Natural Resources Canada, Ottawa (Canada) and Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada)]. E-mail: zwronski@nrcan.gc.ca; Varin, R.A. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Chiu, C. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Czujko, T. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Calka, A. [Department of Materials Science and Engineering, University of Wollongong, NSW 2518 (Australia)

    2007-05-31

    Mechanical alloying of magnesium metal powders with hydrogen in specialized hydrogen ball mills can be used as a direct route for mechanochemical synthesis of emerging chemical hydrides and hydride mixtures for advanced solid-state hydrogen storage. In the 2Mg-Fe system, we have successfully synthesized the ternary complex hydride Mg{sub 2}FeH{sub 6} in a mixture with nanometric Fe particles. The mixture of complex magnesium-iron hydride and nano-iron released 3-4 wt.%H{sub 2} in a thermally programmed desorption experiment at the range 285-295 {sup o}C. Milling of the Mg-2Al powder mixture revealed a strong competition between formation of the Al(Mg) solid solution and the {beta}-MgH{sub 2} hydride. The former decomposes upon longer milling as the Mg atoms react with hydrogen to form the hydride phase, and drive the Al out of the solid solution. The mixture of magnesium dihydride and nano-aluminum released 2.1 wt.%H{sub 2} in the temperature range 329-340 {sup o}C in the differential scanning calorimetry experiment. The formation of MgH{sub 2} was suppressed in the Mg-B system; instead, a hydrogenated amorphous phase (Mg,B)H {sub x}, was formed in a mixture with nanometric MgB{sub 2}. Annealing of the hydrogen-stabilized amorphous mixture produced crystalline MgB{sub 2}.

  14. Metal Hydrides for High-Temperature Power Generation

    Directory of Open Access Journals (Sweden)

    Ewa C. E. Rönnebro

    2015-08-01

    Full Text Available Metal hydrides can be utilized for hydrogen storage and for thermal energy storage (TES applications. By using TES with solar technologies, heat can be stored from sun energy to be used later, which enables continuous power generation. We are developing a TES technology based on a dual-bed metal hydride system, which has a high-temperature (HT metal hydride operating reversibly at 600–800 °C to generate heat, as well as a low-temperature (LT hydride near room temperature that is used for hydrogen storage during sun hours until there is the need to produce electricity, such as during night time, a cloudy day or during peak hours. We proceeded from selecting a high-energy density HT-hydride based on performance characterization on gram-sized samples scaled up to kilogram quantities with retained performance. COMSOL Multiphysics was used to make performance predictions for cylindrical hydride beds with varying diameters and thermal conductivities. Based on experimental and modeling results, a ~200-kWh/m3 bench-scale prototype was designed and fabricated, and we demonstrated the ability to meet or exceed all performance targets.

  15. The use of metal hydrides in fuel cell applications

    Directory of Open Access Journals (Sweden)

    Mykhaylo V. Lototskyy

    2017-02-01

    Full Text Available This paper reviews state-of-the-art developments in hydrogen energy systems which integrate fuel cells with metal hydride-based hydrogen storage. The 187 reference papers included in this review provide an overview of all major publications in the field, as well as recent work by several of the authors of the review. The review contains four parts. The first part gives an overview of the existing types of fuel cells and outlines the potential of using metal hydride stores as a source of hydrogen fuel. The second part of the review considers the suitability and optimisation of different metal hydrides based on their energy efficient thermal integration with fuel cells. The performances of metal hydrides are considered from the viewpoint of the reversible heat driven interaction of the metal hydrides with gaseous H2. Efficiencies of hydrogen and heat exchange in hydrogen stores to control H2 charge/discharge flow rates are the focus of the third section of the review and are considered together with metal hydride – fuel cell system integration issues and the corresponding engineering solutions. Finally, the last section of the review describes specific hydrogen-fuelled systems presented in the available reference data.

  16. Single walled carbon nanotubes functionalized with hydrides as potential hydrogen storage media: A survey of intermolecular interactions

    Energy Technology Data Exchange (ETDEWEB)

    Surya, V.J.; Iyakutti, K. [School of Physics, Madurai Kamaraj University, Madurai, Tamil Nadu (India); Venkataramanan, N.S.; Mizuseki, H.; Kawazoe, Y. [Institute for Materials Research, Tohoku University, Katahira Aoba-ku, Sendai (Japan)

    2011-09-15

    In this paper, we have analyzed the intermolecular interactions between H{sub 2} and single walled carbon nanotube (SWCNT)-hydride complexes and project their capability as a practicable hydrogen storage medium (HSM). In this respect, we have investigated the type of interactions namely van der Waals, electrostatic, and orbital interactions to understand the molecular hydrogen binding affinity of various systems. We found that the charge transfer effects coupled with induced electrostatic interactions are responsible for synergetic action of SWCNT and hydrides on adsorption of H{sub 2} molecules at ambient conditions. Also we have calculated the thermodynamically usable capacity of hydrogen in all the systems. This study enables one to identify and design potential hydrogen storage materials. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Metallographic and fractographic observations of hydrides during delayed hydride cracking in Zr-2.5% Nb alloy

    Energy Technology Data Exchange (ETDEWEB)

    Jovanovic, M.T.; Eadie, R.L. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Chemical and Materials Engineering; Shek, G.K.; Seahra, H. [Ontario Hydro Technologies, Toronto, Ontario (Canada)

    1998-01-01

    Potential drop measurements, optical microscopy, and scanning electron microscopy were performed to study the mechanism of delayed hydride cracking (DHC), the relation of the fracture to the hydride morphology, and the fractography of the DHC mechanism. The material used in this study was taken from modified extrusions of the material used to manufacture Zr-2.5% Nb pressure tubes. The material was electrolytically hydrided to approximately 60 {micro}g/g before testing. Cracking tests were carried out at 250 C with an applied K{sub 1} of 12 MPa {radical}m. The number of potential jumps was strongly correlated to the number of striations on the fracture surface. The results indicate that the DHC process occurs in these samples in an intermittent fashion. Brittle fracture is the operating fracture mechanism for the hydrides that cover most of the fracture surface, but there are some regions of ductile fracture both within the fracture and at the striations.

  18. In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

    Science.gov (United States)

    Yang, Xiao Guang; Liaw, Bor Yann

    Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

  19. Kinetic Resolution of Aryl Alkenylcarbinols Catalyzed by Fc-PIP

    Institute of Scientific and Technical Information of China (English)

    胡斌; 孟萌; 姜山山; 邓卫平

    2012-01-01

    An effective kinetic resolution of a variety of aryl alkenylcarbinols catalyzed by nonenzymatic acyl transfer catalyst Fe-PIP was developed, affording corresponding unreacted alcohols in good to excellent ee value up to 99% and with selectivity factors up to 24.

  20. A quantitative phase field model for hydride precipitation in zirconium alloys: Part II. Modeling of temperature dependent hydride precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Zhihua [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); PolyU Base (Shenzhen) Limited, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Hao, Mingjun [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Guo, Xianghua [State Key Laboratory of Explosion and Safety Science, Beijing Institute of Technology, Beijing 100081 (China); Tang, Guoyi [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Shi, San-Qiang, E-mail: mmsqshi@polyu.edu.hk [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); PolyU Base (Shenzhen) Limited, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China)

    2015-04-15

    A quantitative free energy functional developed in Part I (Shi and Xiao, 2014 [1]) was applied to model temperature dependent δ-hydride precipitation in zirconium in real time and real length scale. At first, the effect of external tensile load on reorientation of δ-hydrides was calibrated against experimental observations, which provides a modification factor for the strain energy in free energy formulation. Then, two types of temperature-related problems were investigated. In the first type, the effect of temperature transient was studied by cooling the Zr–H system at different cooling rates from high temperature while an external tensile stress was maintained. At the end of temperature transients, the average hydride size as a function of cooling rate was compared to experimental data. In the second type, the effect of temperature gradients was studied in a one or two dimensional temperature field. Different boundary conditions were applied. The results show that the hydride precipitation concentrated in low temperature regions and that it eventually led to the formation of hydride blisters in zirconium. A brief discussion on how to implement the hysteresis of hydrogen solid solubility on hydride precipitation and dissolution in the developed phase field scheme is also presented.

  1. Distortion/interaction analysis reveals the origins of selectivities in iridium-catalyzed C-H borylation of substituted arenes and 5-membered heterocycles

    OpenAIRE

    Green, AG; Liu, P.; Merlic, CA; Houk, KN

    2014-01-01

    The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir-C bond. Consequently, the regioselectivity is mainly controlled by differences in the intera...

  2. Heat exchanger selection and design analyses for metal hydride heat pump systems

    DEFF Research Database (Denmark)

    Mazzucco, Andrea; Voskuilen, Tyler G.; Waters, Essene L.

    2016-01-01

    This study presents a design analysis for the development of highly efficient heat exchangers within stationary metal hydride heat pumps. The design constraints and selected performance criteria are applied to three representative heat exchangers. The proposed thermal model can be applied to select...... the most efficient heat exchanger design and provides outcomes generally valid in a pre-design stage. Heat transfer effectiveness is the principal performance parameter guiding the selection analysis, the results of which appear to be mildly (up to 13%) affected by the specific Nusselt correlation used....... The thermo-physical properties of the heat transfer medium and geometrical parameters are varied in the sensitivity analysis, suggesting that the length of independent tubes is the physical parameter that influences the performance of the heat exchangers the most. The practical operative regions for each...

  3. Designing metal hydride complexes for water splitting reactions: a molecular electrostatic potential approach.

    Science.gov (United States)

    Sandhya, K S; Suresh, Cherumuttathu H

    2014-08-28

    The hydridic character of octahedral metal hydride complexes of groups VI, VII and VIII has been systematically studied using molecular electrostatic potential (MESP) topography. The absolute minimum of MESP at the hydride ligand (Vmin) and the MESP value at the hydride nucleus (VH) are found to be very good measures of the hydridic character of the hydride ligand. The increasing/decreasing electron donating feature of the ligand environment is clearly reflected in the increasing/decreasing negative character of Vmin and VH. The formation of an outer sphere metal hydride-water complex showing the HH dihydrogen interaction is supported by the location and the value of Vmin near the hydride ligand. A higher negative MESP suggested lower activation energy for H2 elimination. Thus, MESP features provided a way to fine-tune the ligand environment of a metal-hydride complex to achieve high hydridicity for the hydride ligand. The applicability of an MESP based hydridic descriptor in designing water splitting reactions is tested for group VI metal hydride model complexes of tungsten.

  4. Palladium(II)-Catalyzed Cross-Dehydrogenative Coupling (CDC) of N-Phthaloyl Dehydroalanine Esters with Simple Arenes: Stereoselective Synthesis of Z-Dehydrophenylalanine Derivatives.

    Science.gov (United States)

    Bartoccini, Francesca; Cannas, Diego Maria; Fini, Francesco; Piersanti, Giovanni

    2016-06-03

    Pd(II)-catalyzed cross-dehydrogenative coupling (CDC) of methyl N-phthaloyl dehydroalanine esters with simple aromatic hydrocarbons is reported. The reaction, which involves the cleavage of two sp(2) C-H bonds followed by C-C bond formation, stereoselectively generates highly valuable Z-dehydrophenylalanine skeletons in a practical, versatile, and atom economical manner. In addition, a perfluorinated product was expediently converted into important nonproteinogenic amino acid building blocks through copper-catalyzed conjugate additions of boron, silicon, and hydride moieties.

  5. Hydriding and Dehydriding Properties of Zinc Borohydride, Nickel, and Titanium-Added Magnesium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Young Jun; Kwon, Sung Nam; Song, Myoung Youp [Chonbuk National University, Jeonju (Korea, Republic of)

    2015-11-15

    A Zn(BH{sub 4}){sub 2} sample was prepared by milling ZnCl{sub 2} and NaBH{sub 4} in a planetary ball mill under Ar gas. This sample contained NaCl. Then, 90 wt% MgH{sub 2}-5 wt% Zn(BH{sub 4}){sub 2}-2.5 wt% Ni-2.5 wt% Ti samples [named 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti] were prepared by milling in a planetary ball mill under H{sub 2} gas. The hydrogen absorption and release properties of the prepared samples were investigated. In particular, the variations of the initial hydriding and dehydriding rates with temperature were examined. SEM micrographs and XRD patterns of 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti after reactive mechanical grinding and after hydriding-dehydriding were also studied. Particle size distributions and BET specific surface areas of 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti after reactive mechanical grinding and after 11 hydriding-dehydriding cycles were analyzed. The 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti had an effective hydrogen storage capacity (the quantity of hydrogen absorbed for 60 min) of near 5 wt% (4.91 wt% at 593 K).

  6. Metal hydride/chemical heat-pump development project. Phase I. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Argabright, T.A.

    1982-02-01

    The metal hydride/chemical heat pump (MHHP) is a chemical heat pump containing two hydrides for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and/or cooling or temperature upgrading over a wide range of input and ambient temperatures. The system can thus be used with a variety of heat sources including waste heat, solar energy or a fossil fuel. The conceptual design of the MHHP was developed. A national market survey including a study of applications and market sectors was conducted. The technical tasks including conceptual development, thermal and mechanical design, laboratory verification of design and material performance, cost analysis and the detailed design of the Engineering Development Test Unit (EDTU) were performed. As a result of the market study, the temperature upgrade cycle of the MHHP was chosen for development. Operating temperature ranges for the upgrader were selected to be from 70 to 110/sup 0/C (160 to 230/sup 0/F) for the source heat and 140 to 190/sup 0/C (280 to 375/sup 0/F) for the product heat. These ranges are applicable to many processes in industries such as food, textile, paper and pulp, and chemical. The hydride pair well suited for these temperatures is LaNi/sub 5//LaNi/sub 4/ /sub 5/Al/sub 0/ /sub 5/. The EDTU was designed for the upgrade cycle. It is a compact finned tube arrangement enclosed in a pressure vessel. This design incorporates high heat transfer and low thermal mass in a system which maximizes the coefficient of performance (COP). It will be constructed in Phase II. Continuation of this effort is recommended.

  7. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  8. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  9. Micro-scale fracture experiments on zirconium hydrides and phase boundaries

    Science.gov (United States)

    Chan, H.; Roberts, S. G.; Gong, J.

    2016-07-01

    Fracture properties of micro-scale zirconium hydrides and phase boundaries were studied using microcantilever testing methods. FIB-machined microcantilevers were milled on cross-sectional surfaces of hydrided samples, with the most highly-stressed regions within the δ-hydride film, within the α-Zr or along the Zr-hydride interface. Cantilevers were notched using the FIB and then tested in bending using a nanoindenter. Load-displacement results show that three types of cantilevers have distinct deformation properties. Zr cantilevers deformed plastically. Hydride cantilevers fractured after a small amount of plastic flow; the fracture toughness of the δ-hydride was found to be 3.3 ± 0.4 MPam1/2 and SEM examination showed transgranular cleavage on the fracture surfaces. Cantilevers notched at the Zr-hydride interface developed interfacial voids during loading, at loads considerably lower than that which initiate brittle fracture of hydrides.

  10. Investigation of Cracked Lithium Hydride Reactor Vessels

    Energy Technology Data Exchange (ETDEWEB)

    bird, e.l.; mustaleski, t.m.

    1999-06-01

    Visual examination of lithium hydride reactor vessels revealed cracks that were adjacent to welds, most of which were circumferentially located in the bottom portion of the vessels. Sections were cut from the vessels containing these cracks and examined by use of the metallograph, scanning electron microscope, and microprobe to determine the cause of cracking. Most of the cracks originated on the outer surface just outside the weld fusion line in the base material and propagated along grain boundaries. Crack depths of those examined sections ranged from {approximately}300 to 500 {micro}m. Other cracks were reported to have reached a maximum depth of 1/8 in. The primary cause of cracking was the creation of high tensile stresses associated with the differences in the coefficients of thermal expansion between the filler metal and the base metal during operation of the vessel in a thermally cyclic environment. This failure mechanism could be described as creep-type fatigue, whereby crack propagation may have been aided by the presence of brittle chromium carbides along the grain boundaries, which indicates a slightly sensitized microstructure.

  11. Transition-Metal Hydride Radical Cations.

    Science.gov (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  12. Comparison of the interactions in the rare gas hydride and Group 2 metal hydride anions.

    Science.gov (United States)

    Harris, Joe P; Manship, Daniel R; Breckenridge, W H; Wright, Timothy G

    2014-02-28

    We study both the rare gas hydride anions, RG-H(-) (RG = He-Rn) and Group 2 (Group IIa) metal hydride anions, MIIaH(-) (MIIa = Be-Ra), calculating potential energy curves at the CCSD(T) level with augmented quadruple and quintuple basis sets, and extrapolating the results to the basis set limit. We report spectroscopic parameters obtained from these curves; additionally, we study the Be-He complex. While the RG-H(-) and Be-He species are weakly bound, we show that, as with the previously studied BeH(-) and MgH(-) species, the other MIIaH(-) species are strongly bound, despite the interactions nominally also being between two closed shell species: M(ns(2)) and H(-)(1s(2)). We gain insight into the interactions using contour plots of the electron density changes and population analyses. For both series, the calculated dissociation energy is significantly less than the ion/induced-dipole attraction term, confirming that electron repulsion is important in these species; this effect is more dramatic for the MIIaH(-) species than for RG-H(-). Our analyses lead us to conclude that the stronger interaction in the case of the MIIaH(-) species arises from sp and spd hybridization, which allows electron density on the MIIa atom to move away from the incoming H(-).

  13. Multidimensional simulations of hydrides during fuel rod lifecycle

    Science.gov (United States)

    Stafford, D. S.

    2015-11-01

    In light water reactor fuel rods, waterside corrosion of zirconium-alloy cladding introduces hydrogen into the cladding, where it is slightly soluble. When the solubility limit is reached, the hydrogen precipitates into crystals of zirconium hydride which decrease the ductility of the cladding and may lead to cladding failure during dry storage or transportation events. The distribution of the hydride phase and the orientation of the crystals depend on the history of the spatial temperature and stress profiles in the cladding. In this work, we have expanded the existing hydride modeling capability in the BISON fuel performance code with the goal of predicting both global and local effects on the radial, azimuthal and axial distribution of the hydride phase. We compare results from 1D simulations to published experimental data. We demonstrate the new capability by simulating in 2D a fuel rod throughout a lifecycle that includes irradiation, short-term storage in the spent fuel pool, drying, and interim storage in a dry cask. Using the 2D simulations, we present qualitative predictions of the effects of the inter-pellet gap and the drying conditions on the growth of a hydride rim.

  14. The effect of stress state on zirconium hydride reorientation

    Science.gov (United States)

    Cinbiz, Mahmut Nedim

    Prior to storage in a dry-cask facility, spent nuclear fuel must undergo a vacuum drying cycle during which the spent fuel rods are heated up to elevated temperatures of ≤ 400°C to remove moisture the canisters within the cask. As temperature increases during heating, some of the hydride particles within the cladding dissolve while the internal gas pressure in fuel rods increases generating multi-axial hoop and axial stresses in the closed-end thin-walled cladding tubes. As cool-down starts, the hydrogen in solid solution precipitates as hydride platelets, and if the multiaxial stresses are sufficiently large, the precipitating hydrides reorient from their initial circumferential orientation to radial orientation. Radial hydrides can severely embrittle the spent nuclear fuel cladding at low temperature in response to hoop stress loading. Because the cladding can experience a range of stress states during the thermo-mechanical treatment induced during vacuum drying, this study has investigated the effect of stress state on the process of hydride reorientation during controlled thermo-mechanical treatments utilizing the combination of in situ X-ray diffraction and novel mechanical testing analyzed by the combination of metallography and finite element analysis. The study used cold worked and stress relieved Zircaloy-4 sheet containing approx. 180 wt. ppm hydrogen as its material basis. The failure behavior of this material containing radial hydrides was also studied over a range of temperatures. Finally, samples from reactor-irradiated cladding tubes were examined by X-ray diffraction using synchrotron radiation. To reveal the stress state effect on hydride reorientation, the critical threshold stress to reorient hydrides was determined by designing novel mechanical test samples which produce a range of stress states from uniaxial to "near-equibiaxial" tension when a load is applied. The threshold stress was determined after thermo-mechanical treatments by

  15. Sodium-based hydrides for thermal energy applications

    Science.gov (United States)

    Sheppard, D. A.; Humphries, T. D.; Buckley, C. E.

    2016-04-01

    Concentrating solar-thermal power (CSP) with thermal energy storage (TES) represents an attractive alternative to conventional fossil fuels for base-load power generation. Sodium alanate (NaAlH4) is a well-known sodium-based complex metal hydride but, more recently, high-temperature sodium-based complex metal hydrides have been considered for TES. This review considers the current state of the art for NaH, NaMgH3- x F x , Na-based transition metal hydrides, NaBH4 and Na3AlH6 for TES and heat pumping applications. These metal hydrides have a number of advantages over other classes of heat storage materials such as high thermal energy storage capacity, low volume, relatively low cost and a wide range of operating temperatures (100 °C to more than 650 °C). Potential safety issues associated with the use of high-temperature sodium-based hydrides are also addressed.

  16. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  17. Synthesis of New Silicon-linked Lanthanocene Complexes and Their High Catalytic Activity for Methyl Methacrylate Polymerization with Nanometric Sodium Hydride as Co-catalyst

    Institute of Scientific and Technical Information of China (English)

    谢小敏; 黄吉玲

    2005-01-01

    The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.

  18. Determination of arsenic and selenium by hydride generation and headspace solid phase microextraction coupled with optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tyburska, Anna; Jankowski, Krzysztof, E-mail: kj@ch.pw.edu.pl; Rodzik, Agnieszka

    2011-07-15

    A hydride generation headspace solid phase microextraction technique has been developed in combination with optical emission spectrometry for determination of total arsenic and selenium. Hydrides were generated in a 10 mL volume septum-sealed vial and subsequently collected onto a polydimethylsiloxane/Carboxen solid phase microextraction fiber from the headspace of sample solution. After completion of the sorption, the fiber was transferred into a thermal desorption unit and the analytes were vaporized and directly introduced into argon inductively coupled plasma or helium microwave induced plasma radiation source. Experimental conditions of hydride formation reaction as well as sorption and desorption of analytes have been optimized showing the significant effect of the type of the solid phase microextraction fiber coating, the sorption time and hydrochloric acid concentration of the sample solution on analytical characteristics of the method developed. The limits of detection of arsenic and selenium were 0.1 and 0.8 ng mL{sup -1}, respectively. The limit of detection of selenium could be improved further using biosorption with baker's yeast Saccharomyces cerevisiae for analyte preconcentration. The technique was applied for the determination of total As and Se in real samples.

  19. Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters

    NARCIS (Netherlands)

    Intemann, J.; Sirsch, Peter; Harder, Sjoerd

    2014-01-01

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the

  20. Use of triammonium salt of aurin tricarboxylic acid as risk mitigant for aluminum hydride

    Science.gov (United States)

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

    2017-08-08

    A process and a resulting product by process of an aluminum hydride which is modified with by physically combining in a ball milling process an aluminum hydride with a triammonium salt of aurin tricarboxylic acid. The resulting product is an aluminum hydride which is resistant to air, ambient moisture, and liquid water while maintaining useful hydrogen storage and release kinetics.

  1. Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters

    NARCIS (Netherlands)

    Intemann, J.; Sirsch, Peter; Harder, Sjoerd

    2014-01-01

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the

  2. Investigation of metal hydride materials as hydrogen reservoirs for metal-hydrogen batteries

    Science.gov (United States)

    ONISCHAK

    1976-01-01

    The performance and suitability of various metal hydride materials were examined for use as possible hydrogen storage reservoirs for secondary metal-hydrogen batteries. Lanthanum pentanickel hydride appears as a probable candidate in terms of stable hydrogen supply under feasible thermal conditions. A kinetic model describing the decomposition rate data of the hydride has been developed.

  3. Cerium-Hydride Secondary Building Units in a Porous Metal–Organic Framework for Catalytic Hydroboration and Hydrophosphination

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Pengfei; Sawano, Takahiro; Lin, Zekai; Urban, Ania; Boures, Dean; Lin, Wenbin

    2016-11-16

    We report the stepwise, quantitative transformation of CeIV6(μ3-O)4(μ3-OH)4(OH)6(OH2)6 nodes in a new Ce-BTC (BTC = trimesic acid) metal–organic framework (MOF) into the first CeIII6(μ3-O)4(μ3-OLi)4(H)6(THF)6Li6 metal-hydride nodes that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance and electron density compared to homogeneous organolanthanide catalysts, which likely accounts for the unique 1,4-regioselectivity for the hydroboration of pyridine derivatives. MOF nodes can thus be directly transformed into novel single-site solid catalysts without homogeneous counterparts for sustainable chemical synthesis.

  4. Cerium-Hydride Secondary Building Units in a Porous Metal-Organic Framework for Catalytic Hydroboration and Hydrophosphination.

    Science.gov (United States)

    Ji, Pengfei; Sawano, Takahiro; Lin, Zekai; Urban, Ania; Boures, Dean; Lin, Wenbin

    2016-11-16

    We report the stepwise, quantitative transformation of Ce(IV)6(μ3-O)4(μ3-OH)4(OH)6(OH2)6 nodes in a new Ce-BTC (BTC = trimesic acid) metal-organic framework (MOF) into the first Ce(III)6(μ3-O)4(μ3-OLi)4(H)6(THF)6Li6 metal-hydride nodes that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance and electron density compared to homogeneous organolanthanide catalysts, which likely accounts for the unique 1,4-regioselectivity for the hydroboration of pyridine derivatives. MOF nodes can thus be directly transformed into novel single-site solid catalysts without homogeneous counterparts for sustainable chemical synthesis.

  5. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production.

    Science.gov (United States)

    Wiedner, Eric S; Bullock, R Morris

    2016-07-06

    A large variety of molecular cobalt complexes are used as electrocatalysts for H2 production, but the key cobalt hydride intermediates are frequently difficult to detect and characterize due to their high reactivity. We report that a combination of variable scan rate cyclic voltammetry and foot-of-the-wave analysis (FOWA) can be used to detect transient Co(III)H and Co(II)H intermediates of electrocatalytic H2 production by [Co(II)(P(tBu)2N(Ph)2)(CH3CN)3](2+) and Co(II)(dmgBF2)2(CH3CN)2. In both cases, reduction of a transient catalytic intermediate occurs at a potential that coincides with the Co(II/I) couple. Each reduction displays quasireversible electron-transfer kinetics, consistent with reduction of a Co(III)H intermediate to Co(II)H, which is then protonated by acid to generate H2. A bridge-protonated Co(I) species was ruled out as a catalytic intermediate for Co(II)(dmgBF2)2(CH3CN)2 from voltammograms recorded at 1000 psi of H2. Density functional theory was used to calculate Co(III)-H and Co(II)-H bond strengths for both catalysts. Despite having very different ligands, the cobalt hydrides of both catalysts possess nearly identical heterolytic and homolytic Co-H bond strengths for the Co(III)H and Co(II)H intermediates.

  6. Hydriding-dehydriding properties of Mg2Ni alloy modified by ball-milling in tetrahydrofuran

    Institute of Scientific and Technical Information of China (English)

    CHEN Changpin; WANG Wei; CHEN Yun; CHEN Lixin; WANG Qidong

    2004-01-01

    A new approach of ball-milled Mg2Ni in tetrahydrofuran (THF) to improve the hydriding kinetics of Mg2Ni alloy is suggested and studied. It is found that the modified alloy displayed the improved activity for hydriding even at relatively low temperature (e.g., 323-373 K). In the case of the sample milled in THF for 20 h, the hydrogen content (mass fraction)reaches 1.6 % at 323 K, 2.1% at 348 K and 3.4% at 448 K, respectively. The use of THF during grinding led to the change of the structure, which is reflected by the broadening and weakening of the diffraction peaks in the XRD spectra. The XPS analysis shows that Mg (2s) binding energy peak of Mg2Ni after modification shifted from a lower binding energy to a higher one, indicating the charge transference between Mg and THF and the formation of catalytically active electron donor-acceptor (EDA) complexes on the surface of modified Mg2Ni alloy.

  7. The mechanism of the NHC catalyzed aza-Morita-Baylis-Hillman reaction: insights into a new substrate-catalyzed bimolecular pathway.

    Science.gov (United States)

    Verma, Pritha; Verma, Pragya; Sunoj, Raghavan B

    2014-04-14

    The first mechanistic study on the NHC-catalyzed aza-MBH reaction between cyclopentenone and N-mesylbenzaldimine using density functional theory reveals that a bimolecular mechanism, involving two molecules of benzaldimine in the proton transfer, is energetically more preferred over the conventional direct proton transfer.

  8. Simultaneous determination of hydride and non-hydride forming elements by inductively coupled plasma optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Benzo, Z. [Instituto Venezolano de Investigaciones Cientificas, IVIC, Altos de Pipe, Caracas (Venezuela, Bolivarian Republic of); Matos-Reyes, M.N.; Cervera, M.L.; Guardia, M. de la, E-mail: m.luisa.cervera@uv.es [Department of Analytical Chemistry, University of Valencia, Valencia (Spain)

    2011-09-15

    The operating characteristics of a dual nebulization system were studied including instrumental and chemical conditions for the hydride generation and analytical figures of merit for both, hydride and non hydride forming elements. Analytical performance of the nebulization system was characterized by detection limits from 0.002 to 0.0026 {mu}g mL{sup -1} for the hydride forming elements and between 0.0034 and 0.0121 {mu}g mL{sup -1} for the non-hydride forming elements, relative standard deviation for 10 replicate measurements at 0.25 mg L{sup -1} level and recovery percentages between 97 and 103%. The feasibility of the system was demonstrated in the simultaneous determination of Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Zn, As, Bi, Sb, Se, and Te in the NIST 1549 (non-fat milk powder), NIST 1570a (spinach leaves), DORM-2 (dogfish muscle) and TORT-2 (lobster hepatopancreas) certified samples for trace elements. Results found were in good agreement with the certified ones. (author)

  9. Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

    KAUST Repository

    Werghi, Baraa

    2015-07-17

    Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

  10. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Benjamin W.; Herberg, Julie L. (Lawrence Livermore National Laboratory, Livermore, CA); Highley, Aaron M.; Grossman, Jeffrey (MIT, Cambridge, MA); Wagner, Lucas (MIT, Cambridge, MA); Bhakta, Raghu; Peaslee, D. (University of Missouri, St. Louis, MO); Allendorf, Mark D.; Liu, X. (University of Missouri, St. Louis, MO); Behrens, Richard, Jr.; Majzoub, Eric H. (University of Missouri, St. Louis, MO)

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  11. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    AI Teng; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1.

  12. A nickel metal hydride battery for electric vehicles.

    Science.gov (United States)

    Ovshinsky, S R; Fetcenko, M A; Ross, J

    1993-04-09

    Widespread use of electric vehicles can have significant impact on urban air quality, national energy independence, and international balance of trade. An efficient battery is the key technological element to the development of practical electric vehicles. The science and technology of a nickel metal hydride battery, which stores hydrogen in the solid hydride phase and has high energy density, high power, long life, tolerance to abuse, a wide range of operating temperature, quick-charge capability, and totally sealed maintenance-free operation, is described. A broad range of multi-element metal hydride materials that use structural and compositional disorder on several scales of length has been engineered for use as the negative electrode in this battery. The battery operates at ambient temperature, is made of nontoxic materials, and is recyclable. Demonstration of the manufacturing technology has been achieved.

  13. CO2 hydrogenation on a metal hydride surface.

    Science.gov (United States)

    Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

    2012-04-28

    The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface.

  14. Zirconium hydride formation in Hanford production reactor process tubes

    Energy Technology Data Exchange (ETDEWEB)

    Winegardner, W.K.; Griggs, B.

    1967-12-01

    Examination of Zircaloy-2 process tubes from Hanford Production Reactors has revealed extensive zirconium hydride formation. In general, attack is limited to the downstream portions of tubes where aluminum spacers are located. Most of the hydride platelets are contained in a case or layer on the inner surface of the tube. It is not unusual to find cases 0.004 to 0.005 in. thick. Analyses of the 0.037 in. wall tubes with such cases intact often reveal hydrogen concentrations greater than 1000 ppM. Investigation indicates that the hydriding is the result of galvanic contact between aluminum and Zircaloy-2. The galvanic couple (contact between dissimilar metals in the presence of reactor cooling water which serves as the electrolyte) results in the cathodic charging of hydrogen into the Zircaloy.

  15. Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines

    Institute of Scientific and Technical Information of China (English)

    LI; Ming

    2001-01-01

    [1]Corey, E. J., Bakshi, R. K., Shibata, S., Highly enantioselective borane reduction ketones catalyzed by chiral oxazaborolidines, J. Am. Chem. Soc., 1987, 109:5551-5553.[2]Wallbaum, S., Martens, J., Asymmetric syntheses with chiral oxazaborolidines, Tetrahedron Asymmetry, 1992, 3: 1475-1504.[3]Deloux, L., Srebnik, M., Asymmetric borane-catalyzed reactions, Chem. Rev., 1993, 93: 763-784.[4]Togni, A., Venanzi, L. M., Nitrogen donors in organometallic chemistry and in homogeneous catalysis, Angew Chem. Int. Ed. Engl., 1994, 33: 497-562.[5]Ager, D. J., Prakash, I., Schaad, D. R., 1,2-amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis, Chem. Rev., 1996, 96: 835-875.[6]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 4. On the hydride transfer in ketone complexes of borane adducts of oxazaborolidines and regeneration of catalyst, Tetrahedron Asymmetry, 1991, 2:1133-1155.[7]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 8. On the conformational freedom of the ketone of ketone-borane complexes of oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry. 1992, 3: 1563-1572.[8]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 7. On the effects controlling the coordination of borane to chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry,1992, 3: 1441-1453.[9]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 12. On the influence of the nature of the ring system on binding in ketone-borane complexes of chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones. Tetrahedron Asymmetry, 1993, 4: 1597-1602.[10]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 19. Strain and stability-oxazadiboretanes potentially involved in the enantioselective reduction of ketones promoted

  16. High-Spin Cobalt Hydrides for Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Patrick L. [Univ. of Rochester, NY (United States)

    2013-08-29

    Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

  17. Phase I. Lanthanum-based Start Materials for Hydride Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gschneidner, K. A. [Ames Lab., Ames, IA (United States); Schmidt, F. A. [Ames Lab., Ames, IA (United States); Frerichs, A. E. [Ames Lab., Ames, IA (United States); Ament, K. A. [Ames Lab., Ames, IA (United States)

    2013-08-20

    The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La1-xRx)(Ni1-yMy)(Siz), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

  18. Review of magnesium hydride-based materials: development and optimisation

    Science.gov (United States)

    Crivello, J.-C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.; Latroche, M.; Milanese, C.; Milčius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    2016-02-01

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the slow rates for some processes such as hydrogen diffusion through the bulk create challenges for large-scale implementation. The present paper reviews fundamentals of the Mg-H system and looks at the recent advances in the optimisation of magnesium hydride as a hydrogen storage material through the use of catalytic additives, incorporation of defects and an understanding of the rate-limiting processes during absorption and desorption.

  19. Hydride formation in core-shell alloyed metal nanoparticles

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2016-07-01

    The model and analysis presented are focused on hydride formation in nanoparticles with a Pd shell and a core formed by another metal. The arrangement of metal atoms is assumed to be coherent (no dislocations). The lattice strain distribution, elastic energy, and chemical potential of hydrogen atoms are scrutinized. The slope of the chemical potential (as a function of hydrogen uptake) is demonstrated to decrease with increasing the core volume, and accordingly the critical temperature for hydride formation and the corresponding hysteresis loops are predicted to decrease as well.

  20. Hydrogen Desorption from Mg Hydride: An Ab Initio Study

    Directory of Open Access Journals (Sweden)

    Simone Giusepponi

    2012-07-01

    Full Text Available Hydrogen desorption from hydride matrix is still an open field of research. By means of accurate first-principle molecular dynamics (MD simulations an Mg–MgH2 interface is selected, studied and characterized. Electronic structure calculations are used to determine the equilibrium properties and the behavior of the surfaces in terms of structural deformations and total energy considerations. Furthermore, extensive ab-initio molecular dynamics simulations are performed at several temperatures to characterize the desorption process at the interface. The numerical model successfully reproduces the experimental desorption temperature for the hydride.

  1. Uranium Hydride Nucleation and Growth Model FY'16 ESC Annual Report

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Mary Ann [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Richards, Andrew Walter [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schulze, Roland K. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-12-20

    Uranium hydride corrosion is of great interest to the nuclear industry. Uranium reacts with water and/or hydrogen to form uranium hydride which adversely affects material performance. Hydride nucleation is influenced by thermal history, mechanical defects, oxide thickness, and chemical defects. Information has been gathered from past hydride experiments to formulate a uranium hydride model to be used in a Canned Subassembly (CSA) lifetime prediction model. This multi-scale computer modeling effort started in FY’13, and the fourth generation model is now complete. Additional high-resolution experiments will be run to further test the model.

  2. Reversible storage of the hydrogen by nano structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Institut Neel et CRETA, CNRS - UJF, 38 - Grenoble (France); Marty, P. [LEGI - INPG, 38 - Grenoble (France)

    2007-07-01

    The magnesium hydride MgH{sub 2} is an excellent hydrogen storage element: low cost, abundant, high mass storage capacity up to 7,6% by weight. Meanwhile it presents slow absorption-desorption kinetics and too high thermodynamical stability. Many studies have been realized to improve these kinetics by co-milling with a transition metal. The author presents the metal transition mechanism of this process and the transfer of the production in the industry. (A.L.B.)

  3. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  4. The influence of hydride on fracture toughness of recrystallized Zircaloy-4 cladding

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Hsiao-Hung, E-mail: 175877@mail.csc.com.tw [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China); China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chiang, Ming-Feng [China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chen, Yen-Chen [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China)

    2014-04-01

    In this work, RXA cladding tubes were hydrogen-charged to target hydrogen content levels between 150 and 800 wppm (part per million by weight). The strings of zirconium hydrides observed in the cross sections are mostly oriented in the circumferential direction. The fracture toughness of hydrided RXA Zircaloy-4 cladding was measured to evaluate its hydride embrittlement susceptibility. With increasing hydrogen content, the fracture toughness of hydrided RXA cladding decreases at both 25 °C and 300 °C. Moreover, highly localized hydrides (forming a hydride rim) aggravate the degradation of the fracture properties of RXA Zircaloy-4 cladding at both 25 °C and 300 °C. Brittle features in the form of quasi-cleavages and secondary cracks were observed on the fracture surface of the hydride rim, even for RXA cladding tested at 300 °C.

  5. Rh-Catalyzed reductive Mannich-type reaction and its application towards the synthesis of (±)-ezetimibe

    Science.gov (United States)

    Isoda, Motoyuki; Sato, Kazuyuki; Kunugi, Yurika; Tokonishi, Satsuki; Tarui, Atsushi; Minami, Hideki

    2016-01-01

    Summary An effective synthesis for syn-β-lactams was achieved using a Rh-catalyzed reductive Mannich-type reaction. A rhodium–hydride complex (Rh–H) derived from diethylzinc (Et2Zn) and a Rh catalyst was used for the 1,4-reduction of an α,β-unsaturated ester to give a Reformatsky-type reagent, which in turn, reacted with an imine to give the syn-β-lactam. Additionally, the reaction was applied to the synthesis of (±)-ezetimibe, a potent β-lactamic cholesterol absorption inhibitor. PMID:27559413

  6. Rh-Catalyzed reductive Mannich-type reaction and its application towards the synthesis of (±-ezetimibe

    Directory of Open Access Journals (Sweden)

    Motoyuki Isoda

    2016-07-01

    Full Text Available An effective synthesis for syn-β-lactams was achieved using a Rh-catalyzed reductive Mannich-type reaction. A rhodium–hydride complex (Rh–H derived from diethylzinc (Et2Zn and a Rh catalyst was used for the 1,4-reduction of an α,β-unsaturated ester to give a Reformatsky-type reagent, which in turn, reacted with an imine to give the syn-β-lactam. Additionally, the reaction was applied to the synthesis of (±-ezetimibe, a potent β-lactamic cholesterol absorption inhibitor.

  7. "Inverse sodium hydride": a crystalline salt that contains H(+) and Na(-).

    Science.gov (United States)

    Redko, Mikhail Y; Vlassa, Mircea; Jackson, James E; Misiolek, Andrzej W; Huang, Rui H; Dye, James L

    2002-05-29

    A crystalline salt has been synthesized that contains H(+) and Na(-) rather than the usual hydride oxidation states of H(-) and Na(+). The key is irreversible encapsulation of H(+) within the cage of 3(6)adamanzane (Adz). The internal proton is kinetically inert to reduction by Na(-) in solution in NH(3)-MeNH(2) mixtures. Synthesis of the sodide is accomplished by a metathesis reaction between Na and AdzH(+)X(-) in which X(-) is a sacrificial anion such as glycolate, isethionate, or nitrate. Reduction or deprotonation of the sacrificial anion forms insoluble byproducts and AdzH(+)Na(-) in solution. After solvent removal, the sodide is dissolved in dimethyl ether and transferred through a frit into a separate chamber for crystallization. The compound was characterized as the sodide by analysis, NMR spectra, and optical absorption spectroscopy.

  8. Electrochemical Studies on LaNi(sub 5-x)Sn(sub x) Metal Hydride Alloys

    Science.gov (United States)

    Ratnakumar, B. V.; Witham, C.; Bowman, R. C., Jr.; Hightower, A.; Fultz, B.

    1996-01-01

    Electrochemical studies were performed on LaNi(sub 5-x)Sn(sub x) with 0(less than or equal to)x(less than or equal to)0.5. We measured the effect of the Sn substituent on the kinetics of charge transfer and diffusion during hydrogen absorption and desorption, and the cyclic lifetimes of LaNi(sub 5-x)Sn(sub x) electrodes in 250 mAh laboratory test cells. We report beneficial effects of making small substitutions of Sn for Ni in LaNi(sub 5) on the performance of metal hydride alloy anode in terms of cyclic lifetime, capacity and kinetics. The optimal concentration of Sn in LaNi(sub 5-x)Sn(sub x) alloys for negative electrodes in alkaline rechargable secondary cells was found to lie in the range 0.25(less than or equal to)x(less than or equal to)0.3.

  9. Manganese Catalyzed C-H Halogenation.

    Science.gov (United States)

    Liu, Wei; Groves, John T

    2015-06-16

    The remarkable aliphatic C-H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon-halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C-H bonds to C-Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L-Mn(V)═O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn-F fluorine source, effecting carbon-fluorine bond formation. Indeed, this idea

  10. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen

  11. Pore confined synthesis of magnesium boron hydride nanoparticles

    NARCIS (Netherlands)

    Au, Yuen S.; Yan, Yigang; De Jong, Krijn P.; Remhof, Arndt; De Jongh, Petra E.

    2014-01-01

    Nanostructured materials based on light elements such as Li, Mg, and Na are essential for energy storage and conversion applications, but often difficult to prepare with control over size and structure. We report a new strategy that is illustrated for the formation of magnesium boron hydrides,

  12. Novel baker's yeast catalysed hydride reduction of an epoxide moiety

    CSIR Research Space (South Africa)

    Horak, RM

    1995-02-27

    Full Text Available -4039(95)00043-7 Tetrahedron Letters, Vol. 36, No. 9, pp. 1541-1544, 1995 Elsevier Science Ltd Printed in Great Britain 0040-4039/95 $9.50+0.00 A Novel Baker's Yeast Catalysed Hydride Reduction of an Epoxide Moiety R. Marthinus Horak, Robin A...

  13. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen stora

  14. Review of magnesium hydride-based materials: development and optimisation

    NARCIS (Netherlands)

    Crivello, J. -C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.; Latroche, M.; Milanese, C.; Milcius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    2016-01-01

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the slo

  15. Process of forming a sol-gel/metal hydride composite

    Science.gov (United States)

    Congdon, James W.

    2009-03-17

    An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

  16. Hydrogen adsorption on palladium and palladium hydride at 1 bar

    DEFF Research Database (Denmark)

    Johansson, Martin; Skulason, Egill; Nielsen, Gunver

    2010-01-01

    The dissociative sticking probability for H-2 on Pd films supported on sputtered Highly Ordered Pyrolytic Graphite (HOPG) has been derived from measurements of the rate of the H-D exchange reaction at 1 bar. The sticking probability for H-2, S. is higher on Pd hydride than on Pd (a factor of 1...

  17. Pore confined synthesis of magnesium boron hydride nanoparticles

    NARCIS (Netherlands)

    Au, Yuen S.; Yan, Yigang; De Jong, Krijn P.; Remhof, Arndt; De Jongh, Petra E.

    2014-01-01

    Nanostructured materials based on light elements such as Li, Mg, and Na are essential for energy storage and conversion applications, but often difficult to prepare with control over size and structure. We report a new strategy that is illustrated for the formation of magnesium boron hydrides, relev

  18. Superconductivity and unexpected chemistry of germanium hydrides under pressure

    Science.gov (United States)

    Davari Esfahani, M. Mahdi; Oganov, Artem R.; Niu, Haiyang; Zhang, Jin

    2017-04-01

    Following the idea that hydrogen-rich compounds might be high-Tc superconductors at high pressures, and the very recent breakthrough in predicting and synthesizing hydrogen sulfide with record-high Tc=203 K , an ab initio evolutionary algorithm for crystal structure prediction was employed to find stable germanium hydrides. In addition to the earlier structure of germane with space group Ama2, we propose a C2/m structure, which is energetically more favorable at pressures above 278 GPa (with inclusion of zero-point energy). Our calculations indicate that the C2/m phase of germane is a superconductor with Tc=67 K at 280 GPa. Germane is found to become thermodynamically unstable to decomposition to hydrogen and the compound Ge3H11 at pressures above 300 GPa. Ge3H11 with space group I 4 ¯m 2 is found to become stable at above 285 GPa with Tc=43 K . We find that the pressure-induced phase stability of germanium hydrides is distinct from analogous isoelectronic systems, e.g., Si hydrides and Sn hydrides. Superconductivity stems from large electron-phonon coupling associated with the wagging, bending, and stretching intermediate-frequency modes derived mainly from hydrogen.

  19. Structural stability of complex hydrides LiBH4 revisited

    DEFF Research Database (Denmark)

    Lodziana, Zbigniew; Vegge, Tejs

    2004-01-01

    A systematic approach to study the phase stability of LiBH4 based on ab initio calculations is presented. Three thermodynamically stable phases are identified and a new phase of Cc symmetry is proposed for the first time for a complex hydride. The x-ray diffraction pattern and vibrational spectra...

  20. Hydride encapsulation by molecular alkali-metal clusters.

    Science.gov (United States)

    Haywood, Joanna; Wheatley, Andrew E H

    2008-07-14

    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  1. Optimizing Misch-Metal Compositions In Metal Hydride Anodes

    Science.gov (United States)

    Bugga, Ratnakumar V.; Halpert, Gerald

    1995-01-01

    Electrochemical cells based on metal hydride anodes investigated experimentally in effort to find anode compositions maximizing charge/discharge-cycle performances. Experimental anodes contained misch metal alloyed with various proportions of Ni, Co, Mn, and Al, and experiments directed toward optimization of composition of misch metal.

  2. Well-defined transition metal hydrides in catalytic isomerizations.

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  3. Nanocrystalline Metal Hydrides Obtained by Severe Plastic Deformations

    Directory of Open Access Journals (Sweden)

    Jacques Huot

    2012-01-01

    Full Text Available It has recently been shown that Severe Plastic Deformation (SPD techniques could be used to obtain nanostructured metal hydrides with enhanced hydrogen sorption properties. In this paper we review the different SPD techniques used on metal hydrides and present some specific cases of the effect of cold rolling on the hydrogen storage properties and crystal structure of various types of metal hydrides such as magnesium-based alloys and body centered cubic (BCC alloys. Results show that generally cold rolling is as effective as ball milling to enhance hydrogen sorption kinetics. However, for some alloys such as TiV0.9Mn1.1 alloy ball milling and cold rolling have detrimental effect on hydrogen capacity. The exact mechanism responsible for the change in hydrogenation properties may not be the same for ball milling and cold rolling. Nevertheless, particle size reduction and texture seems to play a leading role in the hydrogen sorption enhancement of cold rolled metal hydrides.

  4. Metal hydrides for smart window and sensor applications

    NARCIS (Netherlands)

    Yoshimura, K.; Langhammer, C.; Dam, B.

    2013-01-01

    The hydrogenation of metals often leads to changes in optical properties in the visible range. This allows for fundamental studies of the hydrogenation process, as well as the exploration of various applications using these optical effects. Here, we focus on recent developments in metal hydride-base

  5. Tribochemical Decomposition of Light Ionic Hydrides at Room Temperature.

    Science.gov (United States)

    Nevshupa, Roman; Ares, Jose Ramón; Fernández, Jose Francisco; Del Campo, Adolfo; Roman, Elisa

    2015-07-16

    Tribochemical decomposition of magnesium hydride (MgH2) induced by deformation at room temperature was studied on a micrometric scale, in situ and in real time. During deformation, a near-full depletion of hydrogen in the micrometric affected zone is observed through an instantaneous (t MgH2 with reduced crystal size by mechanical deformation.

  6. KNH2-KH: a metal amide-hydride solid solution.

    Science.gov (United States)

    Santoru, Antonio; Pistidda, Claudio; Sørby, Magnus H; Chierotti, Michele R; Garroni, Sebastiano; Pinatel, Eugenio; Karimi, Fahim; Cao, Hujun; Bergemann, Nils; Le, Thi T; Puszkiel, Julián; Gobetto, Roberto; Baricco, Marcello; Hauback, Bjørn C; Klassen, Thomas; Dornheim, Martin

    2016-09-27

    We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2(-) ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

  7. Thin-film metal hydrides for solar energy applications

    Energy Technology Data Exchange (ETDEWEB)

    Mongstad, Trygve Tveiteraas

    2012-11-01

    Thin-film metal hydrides may become important solar energy materials in the future. This thesis demonstrates interesting material properties of metal hydride films, relevant for applications as semiconducting materials for photovoltaic (PV) solar cells and for regulation of light using smart window technology.The work presented here has comprised an experimental study, focusing on three different materials: Magnesium hydride (MgH2), magnesium nickel hydride (Mg2NiH4) and yttrium hydride (YHx). Reactive sputter deposition was used to prepare the metal hydride film samples.This synthesis method is relatively uncommon for metal hydrides. Here,the first demonstration of reactive sputtering synthesis for YHx and Mg2NiH4 is given. Different challenges in forming singlephase, pure metal hydrides were identified: MgH2 could not be deposited without 3-16% metallic Mg present in the films, and YHx was found to react strong-ly to oxygen (O) during the deposition process. On the other hand, Mg2NiH4 films formed easily and apparently without major metallic clusters and with low O content.Mg2NiH4 is a semiconductor with an optical band gap that is suitable for PV solar cells. This study has showed that films with promising electrical and optical properties can be synthesized using reactive cosputtering of Mg and Ni. Using optical methods, the band gap for the as deposited samples was estimated to 1.54-1.76 eV, depending on the Mg-Ni composition. The asdeposited films were amorphous or nano-crystalline, but could be crystallized into the high-temperature fcc structure of Mg2NiH4 using heat treatment at 523 K. The band gap of the crystalline films was 2.1-2.2 eV, depending on the composition.A pronounced photochromic reaction to visible and UV light was observed for transparent yttrium hydride (T-YHx) samples. The optical transmission was reduced when the samples were illuminated, and the original optical transmission was restored when the samples were kept under dark conditions

  8. Activation and discharge kinetics of metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, Stein Egil

    2003-07-01

    Potential step chronoamperometry and Electrochemical Impedance Spectroscopy (eis) measurements were performed on single metal hydride particles. For the {alpha}-phase, the bulk diffusion coefficient and the absorption/adsorption rate parameters were determined. Materials produced by atomisation, melt spinning and conventional casting were investigated. The melt spun and conventional cast materials were identical and the atomised material similar in composition. The particles from the cast and the melt spun material were shaped like parallelepipeds. A corresponding equation, for this geometry, for diffusion coupled to an absorption/adsorption reaction was developed. It was found that materials produced by melt spinning exhibited lower bulk diffusion (1.7E-14 m2/s) and absorption/adsorption reaction rate (1.0E-8 m/s), compared to materials produced by conventionally casting (1.1E-13 m2/s and 5.5E-8 m/s respectively). In addition, the influence of particle active surface and relative diffusion length were discussed. It was concluded that there are uncertainties connected to these properties, which may explain the large distribution in the kinetic parameters measured on metal hydride particles. Activation of metal hydride forming materials has been studied and an activation procedure, for porous electrodes, was investigated. Cathodic polarisation of the electrode during a hot alkaline surface treatment gave the maximum discharge capacity on the first discharge of the electrode. The studied materials were produced by gas atomisation and the spherical shape was retained during the activation. Both an AB{sub 5} and an AB{sub 2} alloy was successfully activated and discharge rate properties determined. The AB{sub 2} material showed a higher maximum discharge capacity, but poor rate properties, compared to the AB{sub 5} material. Reduction of surface oxides, and at the same time protection against corrosion of active metallic nickel, can explain the satisfying results of

  9. Metal Hydrides as hot carrier cell absorber materials

    Science.gov (United States)

    Wang, Pei; Wen, Xiaoming; Shrestha, Santosh; Conibeer, Gavin; Aguey-Zinsou, Kondo-Francois

    2016-09-01

    The hot Carrier Solar Cell (HCSC) allows the photon-induced hot carriers (the carriers with energy larger than the band gap) to be collected before they completely thermalise. The absorber of the HCSC should have a large phononic band gap to supress Klemens Decay, which results in a slow carrier cooling speed. In fact, a large phononic band gap likely exists in a binary compound whose constituent elements have a large mass ratio between each other. Binary hydrides with their overwhelming mass ratio of the constituent elements are important absorber candidates. Study on different types of binary hydrides as potential absorber candidates is presented in this paper. Many binary transition metal hydrides have reported theoretical or experimental phonon dispersion charts which show large phononic band gaps. Among these hydrides, the titanium hydride (TiHX) is outstanding because of its low cost, easy fabrication process and is relatively inert to air and water. A TiHX thin film is fabricated by directly hydrogenating an evaporated titanium thin film. Characterisation shows good crystal quality and the hydrogenation process is believed to be successful. Ultrafast transient absorption (TA) spectroscopy is used to study the electron cooling time of TiHX. The result is very noisy due to the low absorption and transmission of the sample. The evolution of the TA curves has been explained by band to band transition using the calculated band structure of TiH2. Though not reliable due to the high noise, decay time fitting at 700nm and 600nm shows a considerably slow carrier cooling speed of the sample.

  10. Synthesis of hydrides by interaction of intermetallic compounds with ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Tarasov, Boris P., E-mail: tarasov@icp.ac.ru [Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Chernogolovka 142432 (Russian Federation); Fokin, Valentin N.; Fokina, Evelina E. [Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Chernogolovka 142432 (Russian Federation); Yartys, Volodymyr A., E-mail: volodymyr.yartys@ife.no [Institute for Energy Technology, Kjeller NO 2027 (Norway); Department of Materials Science and Engineering, Norwegian University of Science and Technology, Trondheim NO 7491 (Norway)

    2015-10-05

    Highlights: • Interaction of the intermetallics A{sub 2}B, AB, AB{sub 2}, AB{sub 5} and A{sub 2}B{sub 17} with NH{sub 3} was studied. • The mechanism of interaction of the alloys with ammonia is temperature-dependent. • Hydrides, hydridonitrides, disproportionation products or metal–N–H compounds are formed. • NH{sub 4}Cl was used as an activator of the reaction between ammonia and intermetallics. • Interaction with ammonia results in the synthesis of the nanopowders. - Abstract: Interaction of intermetallic compounds with ammonia was studied as a processing route to synthesize hydrides and hydridonitrides of intermetallic compounds having various stoichiometries and types of crystal structures, including A{sub 2}B, AB, AB{sub 2}, AB{sub 5} and A{sub 2}B{sub 17} (A = Mg, Ti, Zr, Sc, Nd, Sm; B = transition metals, including Fe, Co, Ni, Ti and nontransition elements, Al and B). In presence of NH{sub 4}Cl used as an activator of the reaction between ammonia and intermetallic alloys, their interaction proceeds at rather mild P–T conditions, at temperatures 100–200 °C and at pressures of 0.6–0.8 MPa. The mechanism of interaction of the alloys with ammonia appears to be temperature-dependent and, following a rise of the interaction temperature, it leads to the formation of interstitial hydrides; interstitial hydridonitrides; disproportionation products (binary hydride; new intermetallic hydrides and binary nitrides) or new metal–nitrogen–hydrogen compounds like magnesium amide Mg(NH{sub 2}){sub 2}. The interaction results in the synthesis of the nanopowders where hydrogen and nitrogen atoms become incorporated into the crystal lattices of the intermetallic alloys. The nitrogenated materials have the smallest particle size, down to 40 nm, and a specific surface area close to 20 m{sup 2}/g.

  11. Hydride structures in Ti-aluminides subjected to high temperature and hydrogen pressure charging conditions

    Science.gov (United States)

    Legzdina, D.; Robertson, I. M.; Birnbaum, H. K.

    1991-01-01

    The distribution and chemistry of hydrides produced in single and dual phase alloys with a composition near TiAl have been investigated by using a combination of TEM and X-ray diffraction techniques. The alloys were exposed at 650 C to 13.8 MPa of gaseous H2 for 100 h. In the single-phase gamma alloy, large hydrides preferentially nucleated on the grain boundaries and matrix dislocations and a population of small hydrides was distributed throughout the matrix. X-ray and electron diffraction patterns from these hydrides indicated that they have an fcc structure with a lattice parameter of 0.45 nm. EDAX analysis of the hydrides showed that they were enriched in Ti. The hydrides were mostly removed by vacuum annealing at 800 C for 24 h. On dissolution of the hydrides, the chemistry of hydride-free regions of the grain boundary returned to the matrix composition, suggesting that Ti segregation accompanied the hydride formation rather than Ti enrichment causing the formation of the hydride.

  12. Hydriding performances and modeling of a small-scale ZrCo bed

    Energy Technology Data Exchange (ETDEWEB)

    Koo, D.; Lee, J.; Park, J.; Paek, S.; Chung, H. [KAERI-UST, Yuseong, Daejeon (Korea, Republic of); Chang, M.H.; Yun, S.H.; Cho, S.; Jung, K.J. [NFRI, Yuseong, Daejeon (Korea, Republic of)

    2015-03-15

    In order to evaluate the performance of the hydriding of a ZrCo bed, a small-scale getter bed of ZrCo was designed and fabricated. The results show that the hydriding time at room temperature was somewhat shorter than that at higher temperatures of ZrCo and that the performance of hydriding at low temperatures of ZrCo was better than that at high temperatures of ZrCo. The experimental results of the hydrogen pressure of hydriding (ZrCoH{sub 2.8}) at different temperatures were in agreement with the computed values using a numerical modeling equation but with a small difference during the first 10 minutes of the hydriding of ZrCo. The model is based on the Kozeny-Carman equation. The effect of a helium blanket on hydriding was measured and analyzed. The hydriding with no helium blanket in the primary vessel of ZrCo is much faster than that with a helium blanket. The hydriding at a helium concentration of 8% is slower than that at 0%. As the helium concentration increases, the hydriding of ZrCo decreases. The experimental results of the hydriding with 0 %, 4%, and 8% of helium concentration are in agreement with the calculated values but with minimal differences during the first 10 minutes.

  13. Dissociation potential curves of low-lying states in transition metal hydrides. 3. Hydrides of groups 6 and 7.

    Science.gov (United States)

    Koseki, Shiro; Matsushita, Takeshi; Gordon, Mark S

    2006-02-23

    The dissociation curves of low-lying spin-mixed states in monohydrides of groups 6 and 7 were calculated by using an effective core potential (ECP) approach. This approach is based on the multiconfiguration self-consistent field (MCSCF) method, followed by first-order configuration interaction (FOCI) calculations, in which the method employs an ECP basis set proposed by Stevens and co-workers (SBKJC) augmented by a set of polarization functions. Spin-orbit coupling (SOC) effects are estimated within the one-electron approximation by using effective nuclear charges, since SOC splittings obtained with the full Breit-Pauli Hamitonian are underestimated when ECP basis sets are used. The ground states of group 6 hydrides have Omega = (1)/(2)(X(6)Sigma(+)(1/2)), where Omega is the z component of the total angular momentum quantum number. Although the ground states of group 7 hydrides have Omega = 0(+), their main adiabatic components are different; the ground state in MnH originates from the lowest (7)Sigma(+), while in TcH and ReH the main component of the ground state is the lowest (5)Sigma(+). The present paper reports a comprehensive set of theoretical results including the dissociation energies, equilibrium distances, electronic transition energies, harmonic frequencies, anharmonicities, and rotational constants for several low-lying spin-mixed states in these hydrides. Transition dipole moments were also computed among the spin-mixed states and large peak positions of electronic transitions are suggested theoretically for these hydrides. The periodic trends of physical properties of metal hydrides are discussed, based on the results reported in this and other recent studies.

  14. Heavy hydrides: H2Te ultraviolet photochemistry

    Science.gov (United States)

    Underwood, J.; Chastaing, D.; Lee, S.; Wittig, C.

    2005-08-01

    The room-temperature ultraviolet absorption spectrum of H2Te has been recorded. Unlike other group-6 hydrides, it displays a long-wavelength tail that extends to 400 nm. Dissociation dynamics have been examined at photolysis wavelengths of 266 nm (which lies in the main absorption feature) and 355 nm (which lies in the long-wavelength tail) by using high-n Rydberg time-of-flight spectroscopy to obtain center-of-mass translational energy distributions for the channels that yield H atoms. Photodissociation at 355 nm yields TeH(Π1/22) selectively relative to the TeH(Π3/22) ground state. This is attributed to the role of the 3A' state, which has a shallow well at large RH-TeH and correlates to H +TeH(Π1/22). Note that the Π1/22 state is analogous to the P1/22 spin-orbit excited state of atomic iodine, which is isoelectronic with TeH. The 3A' state is crossed at large R only by 2A″, with which it does not interact. The character of 3A' at large R is influenced by a strong spin-orbit interaction in the TeH product. Namely, Π1/22 has a higher degree of spherical symmetry than does Π3/22 (recall that I(P1/22) is spherically symmetric), and consequently Π1/22 is not inclined to form either strongly bonding or antibonding orbitals with the H atom. The 3A'←X transition dipole moment dominates in the long-wavelength region and increases with R. Structure observed in the absorption spectrum in the 380-400 nm region is attributed to vibrations on 3A'. The main absorption feature that is peaked at ˜240nm might arise from several excited surfaces. On the basis of the high degree of laboratory system spatial anisotropy of the fragments from 266 nm photolysis, as well as high-level theoretical studies, the main contribution is believed to be due to the 4A″ surface. The 4A″←X transition dipole moment dominates in the Franck-Condon region, and its polarization is in accord with the experimental observations. An extensive secondary photolysis (i.e., of nascent TeH) is

  15. Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.; Dedrick, Daniel E.; Reeder, Craig L.

    2012-02-01

    In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested

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

    OpenAIRE

    Sawadjoon, Supaporn

    2013-01-01

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

  17. Hydrogen cycling of niobium and vanadium catalyzed nanostructured magnesium.

    Science.gov (United States)

    Schimmel, H Gijs; Huot, Jacques; Chapon, Laurent C; Tichelaar, Frans D; Mulder, Fokko M

    2005-10-19

    The reaction of hydrogen gas with magnesium metal, which is important for hydrogen storage purposes, is enhanced significantly by the addition of catalysts such as Nb and V and by using nanostructured powders. In situ neutron diffraction on MgNb(0.05) and MgV(0.05) powders give a detailed insight on the magnesium and catalyst phases that exist during the various stages of hydrogen cycling. During the early stage of hydriding (and deuteriding), a MgH(1hydrogen diffusion coefficient, partly explaining the enhanced kinetics of nanostructured magnesium. It is shown that under relevant experimental conditions, the niobium catalyst is present as NbH(1). Second, a hitherto unknown Mg-Nb perovskite phase could be identified that has to result from mechanical alloying of Nb and the MgO layer of the particles. Vanadium is not visible in the diffraction patterns, but electron micrographs show that the V particle size becomes very small, 2-20 nm. Nanostructuring and catalyzing the Mg enhance the adsorption speed that much that now temperature variations effectively limit the absorption speed and not, as for bulk, the slow kinetics through bulk MgH(2) layers.

  18. Is there theoretical evidence for mutual influence between halogen and pnicogen-hydride bonds? An ab initio study

    Indian Academy of Sciences (India)

    ELAHE PARVINI; MORTEZA VATANPARAST; ESMAIL VESSALLY; ALI BAHADORI

    2016-12-01

    Ab initio MP2/6-311++G(d,p) level calculations have been carried out to investigate the interplay between the halogen and pnicogen-hydride bonds in NCX...OPH₃...HMgY complexes (X = F, Cl, Br; Y = F, Cl, Br, H). The results indicated that the cooperative effects are obvious in the target complexes. These effects were considered in detail in terms of electrostatic potential, energetic, geometric, charge-transfer and electron density properties of the complexes. The values of cooperative energy (Ecoop) were ranging from −0.41 to −0.60 kJ/mol, −1.02 to −1.57 kJ/mol and −1.50 to −2.28 kJ/mol for X = F, Cl and Br, respectively. Based on many-body analysis, two and three-body terms of interaction energies have a positive contribution to the total interaction energy. It was found that the amount of charge transfer in the triads is higher than that in the corresponding dyads. AIM analyses showed that the halogen and pnicogen-hydride bonds in the triads are amplified with respect to the dyads

  19. Effect of thermo-mechanical cycling on zirconium hydride reorientation studied in situ with synchrotron X-ray diffraction

    Science.gov (United States)

    Colas, Kimberly B.; Motta, Arthur T.; Daymond, Mark R.; Almer, Jonathan D.

    2013-09-01

    The circumferential hydrides normally present in nuclear reactor fuel cladding after reactor exposure may dissolve during drying for dry storage and re-precipitate when cooled under load into a more radial orientation, which could embrittle the fuel cladding. It is necessary to study the rates and conditions under which hydride reorientation may happen in order to assess fuel integrity in dry storage. The objective of this work is to study the effect of applied stress and thermal cycling on the hydride morphology in cold-worked stress-relieved Zircaloy-4 by combining conventional metallography and in situ X-ray diffraction techniques. Metallography is used to study the evolution of hydride morphology after several thermo-mechanical cycles. In situ X-ray diffraction performed at the Advanced Photon Source synchrotron provides real-time information on the process of hydride dissolution and precipitation under stress during several thermal cycles. The detailed study of diffracted intensity, peak position and full-width at half-maximum provides information on precipitation kinetics, elastic strains and other characteristics of the hydride precipitation process. The results show that thermo-mechanical cycling significantly increases the radial hydride fraction as well as the hydride length and connectivity. The radial hydrides are observed to precipitate at a lower temperature than circumferential hydrides. Variations in the magnitude and range of hydride strains due to reorientation and cycling have also been observed. These results are discussed in light of existing models and experiments on hydride reorientation. The study of hydride elastic strains during precipitation shows marked differences between circumferential and radial hydrides, which can be used to investigate the reorientation process. Cycling under stress above the threshold stress for reorientation drastically increases both the reoriented hydride fraction and the hydride size. The reoriented hydride

  20. FEASIBILITY OF RECYCLING PLUTONIUM AND MINOR ACTINIDES IN LIGHT WATER REACTORS USING HYDRIDE FUEL

    Energy Technology Data Exchange (ETDEWEB)

    Greenspan, Ehud; Todreas, Neil; Taiwo, Temitope

    2009-03-10

    The objective of this DOE NERI program sponsored project was to assess the feasibility of improving the plutonium (Pu) and minor actinide (MA) recycling capabilities of pressurized water reactors (PWRs) by using hydride instead of oxide fuels. There are four general parts to this assessment: 1) Identifying promising hydride fuel assembly designs for recycling Pu and MAs in PWRs 2) Performing a comprehensive systems analysis that compares the fuel cycle characteristics of Pu and MA recycling in PWRs using the promising hydride fuel assembly designs identified in Part 1 versus using oxide fuel assembly designs 3) Conducting a safety analysis to assess the likelihood of licensing hydride fuel assembly designs 4) Assessing the compatibility of hydride fuel with cladding materials and water under typical PWR operating conditions Hydride fuel was found to offer promising transmutation characteristics and is recommended for further examination as a possible preferred option for recycling plutonium in PWRs.

  1. Molecular early main group metal hydrides: synthetic challenge, structures and applications.

    Science.gov (United States)

    Harder, Sjoerd

    2012-11-25

    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](∞) and [MH(2)](∞) salts are high, the synthesis of well-defined soluble hydride complexes is an obvious challenge. Access to molecular early main group metal hydrides, however, is rewarding: these hydrocarbon-soluble metal hydrides are highly reactive, have found use in early main group metal catalysis and are potentially also valuable molecular model systems for polar metal hydrides as a hydrogen storage material. The article focusses specifically on alkali and alkaline-earth metal hydride complexes and discusses the synthetic challenge, molecular structures, reactivity and applications.

  2. Exploring possible reaction pathways for the o-atom transfer reactions to unsaturated substrates catalyzed by a [Ni-NO2 ] ↔ [Ni-NO] redox couple using DFT methods.

    Science.gov (United States)

    Tsipis, Athanassios C

    2017-07-15

    The (nitro)(N-methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO2 )(S2 CNHMe)(PMe3 )] complex catalyses efficiently the O-atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO2 )(S2 CNHMe)(PMe3 )] ↔ Ni(NO2 )(S2 CNHMe)(PMe3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five-member metallacycle intermediate, via a [3 + 2] cyclo-addition reaction of HC≡CH to the Ni-N = O moiety of the Ni(NO2 )(S2 CNHMe)(PMe3 )] complex, followed by a β H-atom migration toward the Cα carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( κN1-NO2 )(S2 CNHMe)(PMe3 )] ⇌ [Ni( κO,O2-ONO)(S2 CNHMe)(PMe3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  3. 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.

  4. Orbital-like motion of hydride ligands around low-coordinate metal centers.

    Science.gov (United States)

    Ortuño, Manuel A; Vidossich, Pietro; Conejero, Salvador; Lledós, Agustí

    2014-12-15

    Hydrogen atoms in the coordination sphere of a transition metal are highly mobile ligands. Here, a new type of dynamic process involving hydrides has been characterized by computational means. This dynamic event consists of an orbital-like motion of hydride ligands around low-coordinate metal centers containing N-heterocyclic carbenes. The hydride movement around the carbene-metal-carbene axis is the lowest energy mode connecting energy equivalent isomers. This understanding provides crucial information for the interpretation of NMR spectra.

  5. High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

    Directory of Open Access Journals (Sweden)

    Borislav Bogdanović

    2009-01-01

    Full Text Available For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

  6. High temperature metal hydrides as heat storage materials for solar and related applications.

    Science.gov (United States)

    Felderhoff, Michael; Bogdanović, Borislav

    2009-01-01

    For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 degrees C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

  7. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    Science.gov (United States)

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  8. Automated determinations of selenium in thermal power plant wastewater by sequential hydride generation and chemiluminescence detection.

    Science.gov (United States)

    Ezoe, Kentaro; Ohyama, Seiichi; Hashem, Md Abul; Ohira, Shin-Ichi; Toda, Kei

    2016-02-01

    After the Fukushima disaster, power generation from nuclear power plants in Japan was completely stopped and old coal-based power plants were re-commissioned to compensate for the decrease in power generation capacity. Although coal is a relatively inexpensive fuel for power generation, it contains high levels (mgkg(-1)) of selenium, which could contaminate the wastewater from thermal power plants. In this work, an automated selenium monitoring system was developed based on sequential hydride generation and chemiluminescence detection. This method could be applied to control of wastewater contamination. In this method, selenium is vaporized as H2Se, which reacts with ozone to produce chemiluminescence. However, interference from arsenic is of concern because the ozone-induced chemiluminescence intensity of H2Se is much lower than that of AsH3. This problem was successfully addressed by vaporizing arsenic and selenium individually in a sequential procedure using a syringe pump equipped with an eight-port selection valve and hot and cold reactors. Oxidative decomposition of organoselenium compounds and pre-reduction of the selenium were performed in the hot reactor, and vapor generation of arsenic and selenium were performed separately in the cold reactor. Sample transfers between the reactors were carried out by a pneumatic air operation by switching with three-way solenoid valves. The detection limit for selenium was 0.008 mg L(-1) and calibration curve was linear up to 1.0 mg L(-1), which provided suitable performance for controlling selenium in wastewater to around the allowable limit (0.1 mg L(-1)). This system consumes few chemicals and is stable for more than a month without any maintenance. Wastewater samples from thermal power plants were collected, and data obtained by the proposed method were compared with those from batchwise water treatment followed by hydride generation-atomic fluorescence spectrometry.

  9. Development of a novel metal hydride-air secondary battery

    Energy Technology Data Exchange (ETDEWEB)

    Gamburzev, S.; Zhang, W.; Velev, O.A.; Srinivasan, S.; Appleby, A.J. [Texas A and M University, College Station (United States). Center for Electrochemical Systems and Hydrogen Research; Visintin, A. [Universidad Nacional de La Plata (Argentina). Insituto Nacional de Investigaciones Fisicoquimica Teoricas y Applicadas

    1998-05-01

    A laboratory metal hydride/air cell was evaluated. Charging was via a bifunctional air gas-diffusion electrode. Mixed nickel and cobalt oxides, supported on carbon black and activated carbon, were used as catalysts in this electrode. At 30 mA cm{sup -2} in 6 M KOH, the air electrode potentials were -0.2 V (oxygen reduction) and +0.65 V (oxygen evolution) vs Hg/HgO. The laboratory cell was cycled for 50 cycles at the C/2 rate (10 mA cm{sup -2}). The average discharge/charge voltages of the cell were 0.65 and 1.6 V, respectively. The initial capacity of the metal hydride electrode decreased by about 15% after 50 cycles. (author)

  10. Detecting low concentrations of plutonium hydride with magnetization measurements

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Wook; Mun, E. D.; Baiardo, J. P.; Zapf, V. S.; Mielke, C. H. [National High Magnetic Field Laboratory, MPA-CMMS, Los Alamos National Laboratory (LANL), Los Alamos, New Mexico 87545 (United States); Smith, A. I.; Richmond, S.; Mitchell, J.; Schwartz, D. [Nuclear Material Science Group, MST-16, LANL, Los Alamos, New Mexico 87545 (United States)

    2015-02-07

    We report the formation of plutonium hydride in 2 at. % Ga-stabilized δ-Pu, with 1 at. % H charging. We show that magnetization measurements are a sensitive, quantitative measure of ferromagnetic plutonium hydride against the nonmagnetic background of plutonium. It was previously shown that at low hydrogen concentrations, hydrogen forms super-abundant vacancy complexes with plutonium, resulting in a bulk lattice contraction. Here, we use magnetization, X-ray, and neutron diffraction measurements to show that in addition to forming vacancy complexes, at least 30% of the H atoms bond with Pu to precipitate PuH{sub x} on the surface of the sample with x ∼ 1.9. We observe magnetic hysteresis loops below 40 K with magnetic remanence, consistent with ferromagnetic PuH{sub 1.9}.

  11. Optical studies of neutron-irradiated lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Oparin, D.V.; Pilipenko, G.I.; Tyutyunnik, O.I.; Gavrilov, F.F.; Sulimov, E.M. (Ural' skij Politekhnicheskij Inst., Sverdlovsk (USSR))

    1984-09-01

    Lithium hydride single crystals irradiated with neutrons were studied by the optical method. Wide bands belonging to the large F-aggregate and quasimetallic F-centres and to the metallic lithium colloids were discovered in the absorption spectra at room temperature. The small Fsub(n)-centres and molecular lithium centres were detected at 77 K. From the electron-vibrational structure of the absorption spectra of these centres the energies of acoustic phonons in X, W, L points of the Brillouin zone of lithium hydride have been found out: TA(L)-235 cm/sup -1/, TA(X)-27g cm/sup -1/, TA(W)-327 cm/sup -1/, LA(W)-384 cm/sup -1/, LA(X)-426 cm/sup -1/.

  12. Hydrorefining distillates from coal liquefaction using intermetallic compound hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kadiev, Kh.M.; Pivovarova, N.A.; Askhabova, Kh.N.; Taramov, Kh.K.

    1986-07-01

    Investigations are discussed into hydrorefining of coal liquefaction distillate using ZrNi intermetallic compound hydride as catalyst. The paper shows that 70-75% reduction in content of unsaturated and sulfur-containing compounds takes place in the presence of this catalyst at low temperature (200-250 C) and pressure (0.1 MPa), and establishes that preliminary preparation of starting material (removal of phenols and nitrous bases) produces significant effect on hydrorefining results and product stability. Tests have also shown that although intermetallic compound hydride catalyst has fairly low stability, it is capable of recovering its catalytic properties on reduction-oxidation treatment. Description of the tests and characteristics of hydrorefining products of coal liquefaction distillate are given. 8 references.

  13. ALUMINUM HYDRIDE: A REVERSIBLE STORAGE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    One of the challenges of implementing the hydrogen economy is finding a suitable solid H{sub 2} storage material. Aluminium (alane, AlH{sub 3}) hydride has been examined as a potential hydrogen storage material because of its high weight capacity, low discharge temperature, and volumetric density. Recycling the dehydride material has however precluded AlH{sub 3} from being implemented due to the large pressures required (>10{sup 5} bar H{sub 2} at 25 C) and the thermodynamic expense of chemical synthesis. A reversible cycle to form alane electrochemically using NaAlH{sub 4} in THF been successfully demonstrated. Alane is isolated as the triethylamine (TEA) adduct and converted to unsolvated alane by heating under vacuum. To complete the cycle, the starting alanate can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride (NaH) This novel reversible cycle opens the door for alane to fuel the hydrogen economy.

  14. Irradiation effects on thermal properties of LWR hydride fuel

    Science.gov (United States)

    Terrani, Kurt; Balooch, Mehdi; Carpenter, David; Kohse, Gordon; Keiser, Dennis; Meyer, Mitchell; Olander, Donald

    2017-04-01

    Three hydride mini-fuel rods were fabricated and irradiated at the MIT nuclear reactor with a maximum burnup of 0.31% FIMA or ∼5 MWd/kgU equivalent oxide fuel burnup. Fuel rods consisted of uranium-zirconium hydride (U (30 wt%)ZrH1.6) pellets clad inside a LWR Zircaloy-2 tubing. The gap between the fuel and the cladding was filled with lead-bismuth eutectic alloy to eliminate the gas gap and the large temperature drop across it. Each mini-fuel rod was instrumented with two thermocouples with tips that are axially located halfway through the fuel centerline and cladding surface. In-pile temperature measurements enabled calculation of thermal conductivity in this fuel as a function of temperature and burnup. In-pile thermal conductivity at the beginning of test agreed well with out-of-pile measurements on unirradiated fuel and decreased rapidly with burnup.

  15. Pyrophoric behaviour of uranium hydride and uranium powders

    Energy Technology Data Exchange (ETDEWEB)

    Le Guyadec, F., E-mail: fabienne.leguyadec@cea.f [CEA Marcoule DEN/DTEC/SDTC, 30207 Bagnols sur Ceze, BP 17171 (France); Genin, X.; Bayle, J.P. [CEA Marcoule DEN/DTEC/SDTC, 30207 Bagnols sur Ceze, BP 17171 (France); Dugne, O. [DEN/DTEC/SGCS, 30207 Bagnols sur Ceze, BP 17171 (France); Duhart-Barone, A.; Ablitzer, C. [CEA Cadarache DEN/DEC/SPUA, 13108 St. Paul lez Durance (France)

    2010-01-31

    Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine powders have been studied and observed in an original and dedicated experimental device placed inside a glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide (<0.5 wt.%) was obtained by heat treatment at low temperature in flowing Ar/5%H{sub 2}. Pure uranium powder was obtained by dehydration in flowing pure argon. Those fine powders showed spontaneous ignition at room temperature in air. An in situ CCD-camera displayed ignition associated with powder temperature measurement. Characterization of powders before and after ignition was performed by XRD measurements and SEM observations. Oxidation mechanisms are proposed.

  16. Reversible metal-hydride phase transformation in epitaxial films.

    Science.gov (United States)

    Roytburd, Alexander L; Boyerinas, Brad M; Bruck, Hugh A

    2015-03-11

    Metal-hydride phase transformations in solids commonly proceed with hysteresis. The extrinsic component of hysteresis is the result of the dissipation of energy of internal stress due to plastic deformation and fracture. It can be mitigated on the nanoscale, where plastic deformation and fracture are suppressed and the transformation proceeds through formation and evolution of coherent phases. However, the phase coherency introduces intrinsic thermodynamic hysteresis, preventing reversible transformation. In this paper, it is shown that thermodynamic hysteresis of coherent metal-hydride transformation can be eliminated in epitaxial film due to substrate constraint. Film-substrate interaction leads to formation of heterophase polydomain nanostructure with variable phase fraction which can change reversibly by varying temperature in a closed system or chemical potential in an open system.

  17. Structural isotope effects in metal hydrides and deuterides.

    Science.gov (United States)

    Ting, Valeska P; Henry, Paul F; Kohlmann, Holger; Wilson, Chick C; Weller, Mark T

    2010-03-07

    Historically the extraction of high-quality crystallographic information from inorganic samples having high hydrogen contents, such as metal hydrides, has involved preparing deuterated samples prior to study using neutron powder diffraction. We demonstrate, through direct comparison of the crystal structure refinements of the binary hydrides SrH(2) and BaH(2) with their deuteride analogues at 2 K and as a function of temperature, that precise and accurate structural information can be obtained from rapid data collections from samples containing in excess of 60 at.% hydrogen using modern high-flux, medium resolution, continuous wavelength neutron powder diffraction instruments. Furthermore, observed isotope-effects in the extracted lattice parameters and atomic positions illustrate the importance of investigating compounds in their natural hydrogenous form whenever possible.

  18. Effects of metastability on hydrogen sorption in fluorine substituted hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Pinatel, E.R.; Corno, M.; Ugliengo, P.; Baricco, M., E-mail: marcello.baricco@unito.it

    2014-12-05

    Highlights: • Fluorine substitution in simple metal hydrides has been modelled. • The stability of the MH{sub (1−x)}F{sub x} solid solutions has been discussed. • Conditions for reversibility of sorption reactions have been suggested. - Abstract: In this work ab initio calculations and Calphad modelling have been coupled to describe the effect of fluorine substitution on the thermodynamics of hydrogenation–dehydrogenation in simple hydrides (NaH, AlH{sub 3} and CaH{sub 2}). These example systems have been used to discuss the conditions required for the formation of a stable hydride–fluoride solid solution necessary to obtain a reversible hydrogenation reaction.

  19. Shielding efficiency of metal hydrides and borohydrides in fusion reactors

    OpenAIRE

    Singh Vishvanath P.; Badiger Nagappa M.; Gerward Leif

    2016-01-01

    Mass attenuation coefficients, mean free paths and exposure buildup factors have been used to characterize the shielding efficiency of metal hydrides and borohydrides, with high density of hydrogen. Gamma ray exposure buildup factors were computed using five-parameter geometric progression fitting at energies 0.015 MeV to15 MeV, and for penetration depths up to 40 mean free paths. Fast-neutron shielding efficiency has been characterized by the effective neu...

  20. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    Science.gov (United States)

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W.; Kiran, Boggavarapu; Bowen, Kit H.

    2016-10-01

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H- and CAl5-7H2- found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  1. METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

    Science.gov (United States)

    Vetrano, J.B.

    1962-01-23

    A method is given for preparing large, sound bodies of delta zirconium hydride. The method includes the steps of heating a zirconium body to a temperature of not less than l000 deg C, providing a hydrogen atmosphere for the zirconium body at a pressure not greater than one atmosphere, reducing the temperature slowly to 800 deg C at such a rate that cracks do not form while maintaining the hydrogen pressure substantially constant, and cooling in an atmosphere of hydrogen. (AEC)

  2. Aluminum Hydride as a Fuel Supplement to NanoThermites

    Science.gov (United States)

    2014-01-01

    explosives and as a hydrogen storage medium. There are as many as six crystalline phases of alane, of which α-alane is themost stable and is also the...a pure nanoaluminum-corresponding metal oxide thermite. As Fig. 2 shows, the addition ofmicron-scale aluminum hydride to a nanoaluminum–copper-oxide... hydrogen does not participate in the thermite reaction. It is quite possible that the hydrogen may react with oxygen and or the metal oxide as an

  3. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Aldridge, F.T.

    1984-05-09

    A study was made of the properties of metal hydrides which may be suitable for use in chromatographic separation of hydrogen isotopes. Sixty-five alloys were measured, with the best having a hydrogen-deuterium separation factor of 1.35 at 60/sup 0/C. Chromatographic columns using these alloys produced deuterium enrichments of up to 3.6 in a single pass, using natural abundance hydrogen as starting material. 25 references, 16 figures, 4 tables.

  4. Synthesis of Renewable Energy Materials, Sodium Aluminum Hydride by Grignard Reagent of Al

    Directory of Open Access Journals (Sweden)

    Jun-qin Wang

    2015-01-01

    Full Text Available The research on hydrogen generation and application has attracted widespread attention around the world. This paper is to demonstrate that sodium aluminum hydride can be synthesized under simple and mild reaction condition. Being activated through organics, aluminum powder reacts with hydrogen and sodium hydride to produce sodium aluminum hydride under atmospheric pressure. The properties and composition of the sample were characterized by FTIR, XRD, SEM, and so forth. The results showed that the product through this synthesis method is sodium aluminum hydride, and it has higher purity, perfect crystal character, better stability, and good hydrogen storage property. The reaction mechanism is also discussed in detail.

  5. Pressure-driven formation and stabilization of superconductive chromium hydrides

    Science.gov (United States)

    Yu, Shuyin; Jia, Xiaojing; Frapper, Gilles; Li, Duan; Oganov, Artem R.; Zeng, Qingfeng; Zhang, Litong

    2015-01-01

    Chromium hydride is a prototype stoichiometric transition metal hydride. The phase diagram of Cr-H system at high pressures remains largely unexplored due to the challenges in dealing with the high activation barriers and complications in handing hydrogen under pressure. We have performed an extensive structural study on Cr-H system at pressure range 0 ∼ 300 GPa using an unbiased structure prediction method based on evolutionary algorithm. Upon compression, a number of hydrides are predicted to become stable in the excess hydrogen environment and these have compositions of Cr2Hn (n = 2–4, 6, 8, 16). Cr2H3, CrH2 and Cr2H5 structures are versions of the perfect anti-NiAs-type CrH with ordered tetrahedral interstitial sites filled by H atoms. CrH3 and CrH4 exhibit host-guest structural characteristics. In CrH8, H2 units are also identified. Our study unravels that CrH is a superconductor at atmospheric pressure with an estimated transition temperature (T c) of 10.6 K, and superconductivity in CrH3 is enhanced by the metallic hydrogen sublattice with T c of 37.1 K at 81 GPa, very similar to the extensively studied MgB2. PMID:26626579

  6. Metal hydride-based thermal energy storage systems

    Energy Technology Data Exchange (ETDEWEB)

    Vajo, John J.; Fang, Zhigang

    2017-10-03

    The invention provides a thermal energy storage system comprising a metal-containing first material with a thermal energy storage density of about 1300 kJ/kg to about 2200 kJ/kg based on hydrogenation; a metal-containing second material with a thermal energy storage density of about 200 kJ/kg to about 1000 kJ/kg based on hydrogenation; and a hydrogen conduit for reversibly transporting hydrogen between the first material and the second material. At a temperature of 20.degree. C. and in 1 hour, at least 90% of the metal is converted to the hydride. At a temperature of 0.degree. C. and in 1 hour, at least 90% of the metal hydride is converted to the metal and hydrogen. The disclosed metal hydride materials have a combination of thermodynamic energy storage densities and kinetic power capabilities that previously have not been demonstrated. This performance enables practical use of thermal energy storage systems for electric vehicle heating and cooling.

  7. Air passivation of metal hydride beds for waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J. E.; Hsu, R. H. [Savannah River National Laboratory, Aiken, SC 29808 (United States)

    2008-07-15

    One waste acceptance criteria for hydride bed waste disposal is that the bed be non-pyrophoric. Batch-wise air ingress tests were performed which determined the amount of air consumed by a metal hydride bed. A desorbed, 4.4 kg titanium prototype hydride storage vessel (HSV) produced a 4.4 deg.C internal temperature rise upon the first air exposure cycle and a 0.1 deg.C temperature rise upon a second air exposure. A total of 346 sec air was consumed by the bed (0.08 sec per gram Ti). A desorbed, 9.66 kg LaNi{sub 4.25}Al{sub 0.75} prototype storage bed experienced larger temperature rises over successive cycles of air ingress and evacuation. The cycles were performed over a period of days with the bed effectively passivated after the 12. cycle. Nine to ten STP-L of air reacted with the bed producing both oxidized metal and water. (authors)

  8. Modellization of Metal Hydride Canister for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Rocio Maceiras

    2015-06-01

    Full Text Available Hydrogen shows very interesting features for its use on-board applications as fuel cell vehicles. This paper presents the modelling of a tank with a metal hydride alloy for on-board applications, which provides good performance under ambient conditions. The metal hydride contained in the tank is Ti0.98Zr0.02V0.43Fe0.09Cr0.05Mn1.5. A two-dimensional model has been performed for the refuelling process (absorption and the discharge process (desorption. For that, individual models of mass balance, energy balance, reaction kinetics and behaviour of hydrogen gas has been modelled. The model has been developed under Matlab / Simulink© environment. Finally, individual models have been integrated into a global model, and simulated under ambient conditions. With the aim to analyse the temperature influence on the state of charge and filling and emptying time, other simulations were performed at different temperatures. The obtained results allow to conclude that this alloy offers a good behaviour with the discharge process under normal ambient conditions. Keywords: Hydrogen storage; metal hydrides; fuel cell; simulation; board applications

  9. Investigation of long term stability in metal hydrides

    Science.gov (United States)

    Marmaro, Roger W.; Lynch, Franklin E.; Chandra, Dhanesh; Lambert, Steve; Sharma, Archana

    1991-01-01

    It is apparent from the literature and the results of this study that cyclic degradation of AB(5) type metal hydrides varies widely according to the details of how the specimens are cycled. The Rapid Cycle Apparatus (RCA) used produced less degradation in 5000 to 10000 cycles than earlier work with a Slow Cycle Apparatus (SCA) produced in 1500 cycles. Evidence is presented that the 453 K (356 F) Thermal Aging (TA) time spent in the saturated condition causes hydride degradation. But increasing the cooling (saturation) period in the RCA did not greatly increase the rate of degradation. It appears that TA type degradation is secondary at low temperatures to another degradation mechanism. If rapid cycles are less damaging than slow cycles when the saturation time is equal, the rate of hydriding/dehydriding may be an important factor. The peak temperatures in the RCA were about 30 C lower than the SCA. The difference in peak cycle temperatures (125 C in the SCA, 95 C in RCA) cannot explain the differences in degradation. TA type degradation is similar to cyclic degradation in that nickel peaks and line broadening are observed in X ray diffraction patterns after either form of degradation.

  10. Performance study of a hydrogen powered metal hydride actuator

    Science.gov (United States)

    Mainul Hossain Bhuiya, Md; Kim, Kwang J.

    2016-04-01

    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 LaNi5 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.

  11. Lewis acid mediated vinyl-transfer reaction of alkynes to N-alkylimines by using the N-alkyl residue as a sacrificial hydrogen donor.

    Science.gov (United States)

    Malakar, Chandi C; Stas, Sara; Herrebout, Wouter; Abbaspour Tehrani, Kourosch

    2013-10-11

    A variety of N-alkyl-α,α-dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)3 or BF3 ⋅OEt2 and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β-dichloroamines. This approach is complementary to previously reported transition-metal-catalyzed vinyl-transfer methods, which are not applicable to aliphatic imines and are restricted to imines that contain an electron-withdrawing nitrogen substituent. In the present approach, terminal alkynes were used as a source of the vinyl residue, and the N-alkyl moiety of the imine acts as a sacrificial hydrogen donor. The additional advantage of this methodology is the fact that no external toxic or hazardous reducing agents or molecular hydrogen has to be used. This new methodology nicely combines a C(sp(2) )C(sp) bond formation, hydride transfer, and an unusual cleavage of an unactivated CN bond, thereby giving rise to functionalized primary allylic amines. A detailed experimental study supported by DFT calculations of the mechanism has been done. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Study on the synthesis of phenoxyacetic acid with the polyethylene glycol-600 by phase transfer catalyzed method%聚乙二醇-600相转移催化合成苯氧乙酸的研究

    Institute of Scientific and Technical Information of China (English)

    程冬梅; 王学明; 张铁军

    2011-01-01

    研究了用杉甲苯作反应介质,在相转移催化剂聚乙二醇-600的作用下,以苯酚、氯乙酸水溶液和氢氧化钠水溶液为原料合成苯氧乙酸的新工艺,较系统地研究了苯酚/氯乙酸摩尔比、催化剂用量、反应时间等因素对产品收率的影响.实验结果表明,最佳条件为:苯酚、氯乙酸摩尔比为1:1.2,催化剂用量占苯酚和氯乙酸的质量百分比为9.5%,在回流状态下反应2.5h.该工艺具有反应条件温和的优点,收率达到83.5%,含量在90%左右.%The new craft of the synthesis of phenoxyacetic acid, which takes phenol, chloroacetic acid and sodium hydroxide water-soluble fluid as the raw material, polyethylene glycol-600 as the phase transfer catalyst and water/toluene as the reaction medium, is studied in this paper. The effects of the molar ratio of phenol and chloroacetic acid, catalyst dosage and reaction time on the yield were studied systematically. The experiment re- suits showed that the optimal reaction conditions are as follows : the molar ratio of phenol to chloroacetic acid is 1:1.2,the quality percentage of catalyst amount in phenol and chloroacetic acid was 9.5% ,and reflux reac- tion time is 2.5 h. The reaction condition was mild, the yield can reach 83.5%, and the content was about 90%.

  13. Sodium hydride precipitation in sodium cold traps

    Energy Technology Data Exchange (ETDEWEB)

    McPheeters, C.C.; Raue, D.J.

    1980-06-01

    A series of experiments have been performed to test a calculational model for precipitation of NaH in sodium cold traps. The calculational model, called ACTMODEL, is a computer simulation that uses the system geometry and operating conditions as input to calculate a mass-transfer coefficient and the distribution of NaH in a cold trap. The ACTMODEL was tested using an analytical cold trap (ACT) that is simple and essentially one-dimensional. The ACT flow and temperature profile can be controlled at any desired condition. The ACT was analyzed destructively after each test to measure the actual NaH distribution. Excellent agreement was obtained between the ACTMODEL simulations and the experiments. Mass-transfer coefficients ranging upward from 6 x 10/sup -5/ m/s were measured in both packless and packed traps. As much as a fourfold increase in precipitation surface area was observed with increasing amount of NaH deposited. 11 figures, 2 tables.

  14. Dual-mode chemical vapor generation for simultaneous determination of hydride-forming and non-hydride-forming elements by atomic fluorescence spectrometry.

    Science.gov (United States)

    Wang, Yu; Xu, Kailai; Jiang, Xiaoming; Hou, Xiandeng; Zheng, Chengbin

    2014-05-21

    A dual-mode chemical vapor generation integrating hydride generation and photochemical vapor generation was developed for simultaneous multi-element analysis of hydride-forming and non-hydride-forming elements by atomic fluorescence spectrometry. Four elements were selected as model elements of hydride-forming (As, Cd) and non-hydride-forming (Ni, Fe) elements to validate this proposed method. Standard or sample solutions were separately pumped to mix with tetrahydroborate, and concentrated formic acid and ammonia, and then directed to a hydride generator and a photochemical reactor to realize simultaneous hydride generation and photochemical vapor generation, respectively. Optimum conditions for dual-mode chemical vapor generation were carefully investigated. Under the optimized conditions, limits of detection of 0.05, 0.008, 0.8 and 0.1 μg L(-1) were obtained for As, Cd, Fe and Ni, respectively. The precisions were 5.0, 5.5, 4.3 and 4.5% (n = 6, RSDs) for 2 μg L(-1) of As, 1 μg L(-1) of Cd, 50 μg L(-1) of Fe and 10 μg L(-1) of Ni, respectively. This method was validated for accuracy with three certified reference water samples and applied to the simultaneous determination of these elements in a tap water sample with spike recoveries in the range of 95-99%.

  15. Gold-Catalyzed Synthesis of Heterocycles

    Science.gov (United States)

    Arcadi, Antonio

    2014-04-01

    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  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. Carbene-metal hydrides can be much less acidic than phosphine-metal hydrides: significance in hydrogenations.

    Science.gov (United States)

    Zhu, Ye; Fan, Yubo; Burgess, Kevin

    2010-05-05

    Acidities of iridium hydride intermediates were shown to be critical in some transformations mediated by the chiral analogues of Crabtree's catalyst, 1-3. To do this, several experiments were undertaken to investigate the acidities of hydrogenation mixtures formed using these iridium-oxazoline complexes. DFT calculations indicated that the acidity difference for Ir-H intermediates in these hydrogenations were astounding; iridium hydride from the N-heterocyclic carbene catalyst 1 was calculated to be around seven pK(a) units less acidic than those from the P-based complexes 2 and 3. Consistent with this, the carbene complex 1 was shown to be more effective for hydrogenations of acid-sensitive substrates. In deuteration experiments, less "abnormal" deuteration was observed, corresponding to fewer complications from acid-mediated alkene isomerization preceding the D(2)-addition step. Finally, simple tests with pH indicators provided visual evidence that phosphine-based catalyst precursors give significantly more acidic reaction mixtures than the corresponding N-heterocyclic carbene ones. These observations indicate carbene-for-phosphine (and similar) ligand substitutions may impact the outcome of catalytic reactions by modifying the acidities of the metal hydrides formed.

  18. Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hardy, B. J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Corgnale, C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Teprovich, J. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Ward, P. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Motyka, Ted [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-01-31

    The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce very high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.

  19. Lewis Acid Catalyzed Benzylic Bromination

    OpenAIRE

    Shibatomi, Kazutaka; Zhang, Yanhua; Yamamoto, Hisashi

    2008-01-01

    Lewis acid catalyzed bromination on aromatic side chain was achieved efficiently by using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) as a bromination reagent under mild conditions. Zirconium(IV) chloride showed the highest catalytic activity for the benzylic bromination. It was revealed that the present Lewis acid catalysis proceeds via the radical generation pathway. In contrast to Lewis acid catalysis, Brønsted acid promoted aromatic ring bromination without any benzylic bromination. Monobro...

  20. Gold-catalyzed domino reactions.

    Science.gov (United States)

    Michelet, Véronique

    2015-01-01

    Gold-catalyzed reactions have appeared to be highly attractive tools for chemists to promote novel transformations to prepare elaborated structures from simple starting materials. This chapter presents selected and original examples of domino processes in the presence of gold catalysts, highlighting reports implying hydration, hydroxylation, and hydroamination as key starting point for cascade transformations. Domino processes implying 1,n-enynes, asymmetric domino transformations, and applications of all the presented processes in total synthesis are presented.

  1. Synthesis of nanocrystalline MgH{sub 2} powder by gas-phase condensation and in situ hydridation: TEM, XPS and XRD study

    Energy Technology Data Exchange (ETDEWEB)

    Friedrichs, O. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain)]. E-mail: veroil@icmse.csic.es; Kolodziejczyk, L. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Sanchez-Lopez, J.C. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Lopez-Cartes, C. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Fernandez, A. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain)

    2007-05-31

    In this work, a two-step method for the preparation of nanocrystalline MgH{sub 2} is presented, where the first step consists of synthesis of nanocrystalline Mg powder by the gas-phase condensation method (GPC) and the second of in situ hydridation leading to the formation of MgH{sub 2} nanoparticles. By transmission electron microscopy (TEM) and electron diffraction (ED), crystalline Mg nanoparticles from GPC were found to have mean size within the range of 30-50 nm, while in the case of MgH{sub 2} nanoparticles these values increase approximately 2-3 times mainly due to particles growth during the hydridation step. The X-ray diffraction (XRD) analysis shows the high conversion into the MgH{sub 2} phase after hydridation. By X-ray photoelectron spectroscopy (XPS) metallic magnesium was detected below a magnesium oxide layer of 3-4 nm for the Mg sample prepared by GPC, which shows the efficiency of a novel sample transfer system without air exposure between N{sub 2}-glove-box, preparation chamber and experimental apparatus.

  2. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri

    2015-11-30

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

  3. Crack initiation at long radial hydrides in Zr-2. 5Nb pressure tube material at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Choubey, R.; Puls, M.P. (AECL Research, Pinawa, Manitoba (Canada). Whiteshell Labs.)

    1994-05-01

    Crack initiation at hydrides in smooth tensile specimens of Zr-2.5Nb pressure tube material was investigated at elevated temperatures up to 300 C using an acoustic emission (AE) technique. The test specimens contained long, radial hydride platelets. These hydrides have their plate normals oriented in the applied stress direction. Below [approximately]100 C, widespread hydride cracking was initiated at stresses close to the yield stress. An estimate of the hydride's fracture strength from this data yielded a value of [approximately]520 MPa at 100 C. Metallography showed that up to this temperature, cracking occurred along the length of the hydrides. However, at higher temperatures, there was no clear evidence of lengthwise cracking of hydrides, and fewer of the total hydride population fractured during deformation, as indicated by the AE record and the metallography. Moreover, the hydrides showed significant plasticity by-being able to flow along with the matrix material and align themselves parallel to the applied stress direction without fracturing. Near the fracture surface of the specimen, transverse cracking of the flow-reoriented hydrides had occurred at various points along the lengths of the hydrides. These fractures appear to be the result of stresses produced by large plastic strains imposed by the surrounding matrix on the less ductile hydrides.

  4. Well-Defined Molecular Magnesium Hydride Clusters : Relationship between Size and Hydrogen-Elimination Temperature

    NARCIS (Netherlands)

    Intemann, Julia; Spielmann, Jan; Sirsch, Peter; Harder, Sjoerd

    A new tetranuclear magnesium hydride cluster, [{NN-(MgH)2}2], which was based on a NN-coupled bis--diketiminate ligand (NN2-), was obtained from the reaction of [{NN-(MgnBu)2}2] with PhSiH3. Its crystal structure reveals an almost-tetrahedral arrangement of Mg atoms and two different sets of hydride

  5. Zirconium hydrides and Fe redistribution in Zr-2.5%Nb alloy under ion irradiation

    Science.gov (United States)

    Idrees, Y.; Yao, Z.; Cui, J.; Shek, G. K.; Daymond, M. R.

    2016-11-01

    Zr-2.5%Nb alloy is used to fabricate the pressure tubes of the CANDU reactor. The pressure tube is the primary pressure boundary for coolant in the CANDU design and is susceptible to delayed hydride cracking, reduction in fracture toughness upon hydride precipitation and potentially hydride blister formation. The morphology and nature of hydrides in Zr-2.5%Nb with 100 wppm hydrogen has been investigated using transmission electron microscopy. The effect of hydrides on heavy ion irradiation induced decomposition of the β phase has been reported. STEM-EDX mapping was employed to investigate the distribution of alloying elements. The results show that hydrides are present in the form of stacks of different sizes, with length scales from nano- to micro-meters. Heavy ion irradiation experiments at 250 °C on as-received and hydrided Zr-2.5%Nb alloy, show interesting effects of hydrogen on the irradiation induced redistribution of Fe. It was found that Fe is widely redistributed from the β phase into the α phase in the as-received material, however, the loss of Fe from the β phase and subsequent precipitation is retarded in the hydrided material. This preliminary work will further the current understanding of microstructural evolution of Zr based alloys in the presence of hydrogen.

  6. Arsenic speciation analysis by HPLC postcolumn hydride generation and detection by atomic fluorescence spectrometry

    OpenAIRE

    Marschner, K; Musil, S. (Stanislav); Rychlovský, P.; Dědina, J. (Jiří)

    2014-01-01

    The aim of this contribution is to present a new method of hydride generation that enables to generate arsines from iAs , iAs , MMA and DMA in a flow injection mode with the same efficiency and in the next step connection of this hydride generator with HPLC column.

  7. Pore-Confined Light Metal Hydrides for Energy Storage and Catalysis

    NARCIS (Netherlands)

    Bramwell, P.L.

    2017-01-01

    Light metal hydrides have enjoyed several decades of attention in the field of hydrogen storage, but their applications have recently begun to diversify more and more into the broader field of energy storage. For example, light metal hydrides have shown great promise as battery materials, in sensors

  8. Study on the Use of Hydride Fuel in High-Performance Light Water Reactor Concept

    Directory of Open Access Journals (Sweden)

    Haileyesus Tsige-Tamirat

    2015-01-01

    Full Text Available Hydride fuels have features which could make their use attractive in future advanced power reactors. The potential benefit of use of hydride fuel in HPLWR without introducing significant modification in the current core design concept of the high-performance light water reactor (HPLWR has been evaluated. Neutronics and thermal hydraulic analyses were performed for a single assembly model of HPLWR with oxide and hydride fuels. The hydride assembly shows higher moderation with softer neutron spectrum and slightly more uniform axial power distribution. It achieves a cycle length of 18 months with sufficient excess reactivity. At Beginning of Cycle the fuel temperature coefficient of the hydride assembly is higher whereas the moderator and void coefficients are lower. The thermal hydraulic results show that the achievable fuel temperature in the hydride assembly is well below the design limits. The potential benefits of the use of hydride fuel in the current design of the HPLWR with the achieved improvements in the core neutronics characteristics are not sufficient to justify the replacement of the oxide fuel. Therefore for a final evaluation of the use of hydride fuels in HPLWR concepts additional studies which include modification of subassembly and core layout designs are required.

  9. First-principles study of superabundant vacancy formation in metal hydrides.

    Science.gov (United States)

    Zhang, Changjun; Alavi, Ali

    2005-07-13

    Recent experiments have established the generality of superabundant vacancies (SAV) formation in metal hydrides. Aiming to elucidate this intriguing phenomenon and to clarify previous interpretations, we employ density-functional theory to investigate atomic mechanisms of SAV formation in fcc hydrides of Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au. We have found that upon H insertion, vacancy formation energies reduce substantially. This is consistent with experimental suggestions. We demonstrate that the entropy effect, which has been proposed to explain SAV formation, is not the main cause. Instead, it is the drastic change of electronic structure induced by the H in the SAV hydrides, which is to a large extent responsible. Interesting trends in systems investigated are also found: ideal hydrides of 5d metals and noble metals are unstable compared to the corresponding pure metals, but the SAV hydrides are more stable than the corresponding ideal hydrides, whereas opposite results exist in the cases of Ni, Rh, and Pd. These trends of stabilities of the SAV hydrides are discussed in detail and a general understanding for SAV formation is provided. Finally, we propose an alternative reaction pathway to generate a SAV hydride from a metal alloy.

  10. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    Science.gov (United States)

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  11. Nickel-Catalyzed Alkoxy-Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers

    KAUST Repository

    Guo, Lin

    2016-11-07

    A nickel-catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B-alkyl 9-BBN and trialkylborane reagents that involves the cleavage of stable C(sp2)−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp2)−C(sp3) bonds that does not suffer from β-hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method.

  12. Palladium(II)-catalyzed intramolecular carboxypalladation-olefin insertion cascade: direct access to indeno[1,2-b]furan-2-ones.

    Science.gov (United States)

    Vinoth, Perumal; Vivekanand, Thavaraj; Suryavanshi, Padmakar A; Menéndez, J Carlos; Sasai, Hiroaki; Sridharan, Vellaisamy

    2015-05-14

    A catalytic, atom-economical, domino 5-endo-dig cyclization-intramolecular olefin insertion sequence was developed under mild conditions. Aryl alkynoic acids bearing a tethered enone partner afforded the indeno[1,2-b]furan-2-ones, the core skeleton present in a number of biologically significant molecules including the natural product solanacol, under ligand-free, palladium-catalyzed reaction conditions in high yields. The competitive β-hydride elimination in the final step leading to the conjugated analogs was avoided by the addition of lithium bromide. A plausible mechanism for this domino sequence is proposed involving intramolecular carboxypalladation and olefin insertion steps.

  13. An exceptional P-H phosphonite: Biphenyl-2,2'-bisfenchylchlorophosphite and derived ligands (BIFOPs in enantioselective copper-catalyzed 1,4-additions

    Directory of Open Access Journals (Sweden)

    Neudörfl J-M

    2005-08-01

    Full Text Available Abstract Biphenyl-2,2'-bisfenchol (BIFOL based chlorophosphite, BIFOP-Cl, exhibits surprisingly high stabilities against hydrolysis as well as hydridic and organometallic nucleophiles. Chloride substitution in BIFOP-Cl proceeds only under drastic conditions. New enantiopure, sterically demanding phosphorus ligands such as a phosphoramidite, a phosphite and a P-H phosphonite (BIFOP-H are hereby accessible. In enantioselective Cu-catalyzed 1,4-additions of ZnEt2 to 2-cyclohexen-1-one, this P-H phosphonite (yielding 65% ee exceeds even the corresponding phosphite and phosphoramidite.

  14. Lactam hydrolysis catalyzed by mononuclear metallo-ß-bactamases

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U

    2003-01-01

    . For most studied systems, the tetrahedral structure is a stable intermediate. Moreover, the C-N bond in the lactam ring is intact in this intermediate, as well as in the following transition state-its cleavage is induced by proton transfer to the nitrogen atom in the lactam ring. However, for the model...... with Asp as a proton shuttle, attack of the zinc-bond hydroxide ion seems to be concerted with the proton transfer. We have also studied the effect of replacing one of the histidine ligands by an asparagine or glutamine residue, giving a zinc site representative of other subclasses of metallo......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...

  15. A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures

    Science.gov (United States)

    Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

    2014-03-01

    Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

  16. Hydrogenation reaction characteristics and properties of its hydrides for magnetic regenerative material HoCu2

    Institute of Scientific and Technical Information of China (English)

    金滔; 吴梦茜; 黄迦乐; 汤珂; 陈立新

    2016-01-01

    The hydrogenation reaction characteristics and the properties of its hydrides for the magnetic regenerative material HoCu2 (CeCu2-type) of a cryocooler were investigated. The XRD testing reveals that the hydrides of HoCu2 were a mixture of Cu, unknown hydride I, and unknown hydride II. Based on the PCT (pressure−concentration−temperature) curves under different reaction temperatures, the relationships among reaction temperature, equilibrium pressure, and maximum hydrogen absorption capacity were analyzed and discussed. The enthalpy changeΔH and entropy changeΔS as a result of the whole hydrogenation process were also calculated from the PCT curves. The magnetization and volumetric specific heat capacity of the hydride were also measured by SQUID magnetometer and PPMS, respectively.

  17. Complex rare-earth aluminum hydrides: mechanochemical preparation, crystal structure and potential for hydrogen storage.

    Science.gov (United States)

    Weidenthaler, Claudia; Pommerin, André; Felderhoff, Michael; Sun, Wenhao; Wolverton, Christopher; Bogdanović, Borislav; Schüth, Ferdi

    2009-11-25

    A novel type of complex rare-earth aluminum hydride was prepared by mechanochemical preparation. The crystal structure of the REAlH(6) (with RE = La, Ce, Pr, Nd) compounds was calculated by DFT methods and confirmed by preliminary structure refinements. The trigonal crystal structure consists of isolated [AlH(6)](3-) octahedra bridged via [12] coordinated RE cations. The investigation of the rare-earth aluminum hydrides during thermolysis shows a decrease of thermal stability with increasing atomic number of the RE element. Rare-earth hydrides (REH(x)) are formed as primary dehydrogenation products; the final products are RE-aluminum alloys. The calculated decomposition enthalpies of the rare-earth aluminum hydrides are at the lower end for reversible hydrogenation under moderate conditions. Even though these materials may require somewhat higher pressures and/or lower temperatures for rehydrogenation, they are interesting examples of low-temperature metal hydrides for which reversibility might be reached.

  18. Strategies for the improvement of the hydrogen storage properties of metal hydride materials.

    Science.gov (United States)

    Wu, Hui

    2008-10-24

    Metal hydrides are an important family of materials that can potentially be used for safe, efficient and reversible on-board hydrogen storage. Light-weight metal hydrides in particular have attracted intense interest due to their high hydrogen density. However, most of these hydrides have rather slow absorption kinetics, relatively high thermal stability, and/or problems with the reversibility of hydrogen absorption/desorption cycling. This paper discusses a number of different approaches for the improvement of the hydrogen storage properties of these materials, with emphasis on recent research on tuning the ionic mobility in mixed hydrides. This concept opens a promising pathway to accelerate hydrogenation kinetics, reduce the activation energy for hydrogen release, and minimize deleterious possible by-products often associated with complex hydride systems.

  19. Getting metal-hydrides to do what you want them to

    Energy Technology Data Exchange (ETDEWEB)

    Gruen, D.M.

    1981-01-01

    With the discovery of AB/sub 5/ compounds, intermetallic hydrides with unusual properties began to be developed (H dissociation pressures of one to several atmospheres, extremely rapid and reversible adsorption/desorption very large amounts of H adsorbed). This paper reviews the factors that must be controlled in order to modify these hydrides to make them useful. The system LaNi/sub 5/ + H/sub 2/ is used as example. Use of AB/sub 5/ hydrides to construct a chemical heat pumps is discussed. Results of a systematic study substituting Al for Ni are reported; the HYCSOS pump is described briefly. Use of hydrides as hydrogen getters (substituted ZrV/sub 2/) is also discussed. Finally, possible developments in intermetallic hydride research in the 1980's and the hydrogen economy are discussed. 10 figures. (DLC)

  20. Evaluation of hydride blisters in zirconium pressure tube in CANDU reactor

    Energy Technology Data Exchange (ETDEWEB)

    Cheong, Y. M.; Kim, Y. S.; Gong, U. S.; Kwon, S. C.; Kim, S. S.; Choo, K.N

    2000-09-01

    When the garter springs for maintaining the gap between the pressure tube and the calandria tube are displaced in the CANDU reactor, the sagging of pressure tube results in a contact to the calandria tube. This causes a temperature difference between the inner and outer surface of the pressure tube. The hydride can be formed at the cold spot of outer surface and the volume expansion by hydride dormation causes the blistering in the zirconium alloys. An incident of pressure tube rupture due to the hydride blisters had happened in the Canadian CANDU reactor. This report describes the theoretical development and models on the formation and growth of hydride blister and some experimental results. The evaluation methodology and non-destructive testing for hydride blister in operating reactors are also described.

  1. Assessing nanoparticle size effects on metal hydride thermodynamics using the Wulff construction.

    Science.gov (United States)

    Kim, Ki Chul; Dai, Bing; Karl Johnson, J; Sholl, David S

    2009-05-20

    The reaction thermodynamics of metal hydrides are crucial to the use of these materials for reversible hydrogen storage. In addition to altering the kinetics of metal hydride reactions, the use of nanoparticles can also change the overall reaction thermodynamics. We use density functional theory to predict the equilibrium crystal shapes of seven metals and their hydrides via the Wulff construction. These calculations allow the impact of nanoparticle size on the thermodynamics of hydrogen release from these metal hydrides to be predicted. Specifically, we study the temperature required for the hydride to generate a H(2) pressure of 1 bar as a function of the radius of the nanoparticle. In most, but not all, cases the hydrogen release temperature increases slightly as the particle size is reduced.

  2. Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides.

    Science.gov (United States)

    Schilter, David; Camara, James M; Huynh, Mioy T; Hammes-Schiffer, Sharon; Rauchfuss, Thomas B

    2016-08-10

    Hydrogenase enzymes efficiently process H2 and protons at organometallic FeFe, NiFe, or Fe active sites. Synthetic modeling of the many H2ase states has provided insight into H2ase structure and mechanism, as well as afforded catalysts for the H2 energy vector. Particularly important are hydride-bearing states, with synthetic hydride analogues now known for each hydrogenase class. These hydrides are typically prepared by protonation of low-valent cores. Examples of FeFe and NiFe hydrides derived from H2 have also been prepared. Such chemistry is more developed than mimicry of the redox-inactive monoFe enzyme, although functional models of the latter are now emerging. Advances in physical and theoretical characterization of H2ase enzymes and synthetic models have proven key to the study of hydrides in particular, and will guide modeling efforts toward more robust and active species optimized for practical applications.

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

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

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

  4. Mathematical modeling of the nickel/metal hydride battery system

    Energy Technology Data Exchange (ETDEWEB)

    Paxton, Blaine Kermit [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering

    1995-09-01

    A group of compounds referred to as metal hydrides, when used as electrode materials, is a less toxic alternative to the cadmium hydroxide electrode found in nickel/cadmium secondary battery systems. For this and other reasons, the nickel/metal hydride battery system is becoming a popular rechargeable battery for electric vehicle and consumer electronics applications. A model of this battery system is presented. Specifically the metal hydride material, LaNi{sub 5}H{sub 6}, is chosen for investigation due to the wealth of information available in the literature on this compound. The model results are compared to experiments found in the literature. Fundamental analyses as well as engineering optimizations are performed from the results of the battery model. In order to examine diffusion limitations in the nickel oxide electrode, a ``pseudo 2-D model`` is developed. This model allows for the theoretical examination of the effects of a diffusion coefficient that is a function of the state of charge of the active material. It is found using present data from the literature that diffusion in the solid phase is usually not an important limitation in the nickel oxide electrode. This finding is contrary to the conclusions reached by other authors. Although diffusion in the nickel oxide active material is treated rigorously with the pseudo 2-D model, a general methodology is presented for determining the best constant diffusion coefficient to use in a standard one-dimensional battery model. The diffusion coefficients determined by this method are shown to be able to partially capture the behavior that results from a diffusion coefficient that varies with the state of charge of the active material.

  5. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    Hydrogen storage is one of the challenges to be overcome for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods. The direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali metal alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  6. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Fewox, C; Ragaiy Zidan, R; Brenda Garcia-Diaz, B

    2008-12-31

    Hydrogen storage is one of the greatest challenges for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods; the direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  7. Effects of Ca additions on some Mg-alloy hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Lupu, D.; Biris, A.; Indrea, E.; Bucur, R.V.

    1983-01-01

    The hydrogenation of the alloy of composition CaMg/sub 1/ /sub 8/Ni/sub 0/ /sub 5/ containing CaMg/sub 2/ and MgNi/sub 2/ shows fast activation kinetics. The Mg/sub 2/Ni phase is observed in the dehydrided samples. The three plateaus on the hydrogen desorption isotherms correspond to the most stable magnesium hydrides observed up to now in Mg-alloy (..delta.. H = 20 to 24 kcal/mol H/sub 2/). The effects of Ca additions on the hydrogen storage capacity and desorption rates of some Mg-rich alloys have been studied. 16 references, 3 figures, 1 table.

  8. Alkyl and Hydride-Olefin Complexes of Niobocene

    NARCIS (Netherlands)

    Klazinga, A.H.; Teuben, J.H.

    1980-01-01

    Reactions of Cp2NbCl2 with RMgCl (R = n-C3H7, i-C3H7, n-C4H9, s-C4H9 and n-C5H11) give niobocene hydride olefin complexes Cp2Nb(H)L (L = C3H6, C4H8 and C5H10). The last step of the reaction probably proceeds via a stereospecific β-H elimination from the monoalkyl species Cp2NbR. Decomposition of n-a

  9. Geoneutrinos and Hydridic Earth (or primordially Hydrogen-Rich Planet)

    CERN Document Server

    Bezrukov, L

    2014-01-01

    Geoneutrino is a new channel of information about geochemical composition of the Earth. We alnalysed here the following problem. What statistics do we need to distinguish between predictions of Bulk Silicate Earth model and Hydridic Earth model for Th/U signal ratio? We obtained the simple formula for estimation of error of Th/U signal ratio. Our calculations show that we need more than $22 kt \\cdot year$ exposition for Gran-Sasso underground laboratory and Sudbury Neutrino Observatory. We need more than $27 kt \\cdot year$ exposition for Kamioka site in the case of stopping of all Japanese nuclear power plants.

  10. Electrochemical process and production of novel complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2013-06-25

    A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

  11. Comparison between different reactions of group IV hydride with H

    Institute of Scientific and Technical Information of China (English)

    ZHANG; Shaolong; ZHANG; Xuqiang; ZHANG; Qinggang; ZHANG; Yici

    2006-01-01

    The four-dimensional time-dependent quantum dynamics calculations for reactions of group IV hydride with H are carried out by employing the semirigid vibrating rotor target model and the time-dependent wave packet method. The reaction possibility, cross section and rate constants for reactions (H+SiH4 and H+GeH4) in different initial vibrational and rotational states are obtained. The common feature for such kind of reaction process is summarized. The theoretical result is consistent with available measurement, which indicates the credibility of this theory and the potential energy surface.

  12. Modeling of Gallium Nitride Hydride Vapor Phase Epitaxy

    Science.gov (United States)

    Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

    1997-01-01

    A reactor model for the hydride vapor phase epitaxy of GaN is presented. The governing flow, energy, and species conservation equations are solved in two dimensions to examine the growth characteristics as a function of process variables and reactor geometry. The growth rate varies with GaCl composition but independent of NH3 and H2 flow rates. A change in carrier gas for Ga source from H2 to N2 affects the growth rate and uniformity for a fixed reactor configuration. The model predictions are in general agreement with observed experimental behavior.

  13. Equilibrium composition for the reaction of plutonium hydride with air

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    There are six independent constituents with 4 chemical elements, i.e. PuH2.7(s), PuN(s), Pu2O3(s), N2, O2 and H2, therefore , the system described involves of 2 independent reactions ,both those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.

  14. Research in Nickel/Metal Hydride Batteries 2016

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2016-10-01

    Full Text Available Nineteen papers focusing on recent research investigations in the field of nickel/metal hydride (Ni/MH batteries have been selected for this Special Issue of Batteries. These papers summarize the joint efforts in Ni/MH battery research from BASF, Wayne State University, the National Institute of Standards and Technology, Michigan State University, and FDK during 2015–2016 through reviews of basic operational concepts, previous academic publications, issued US Patent and filed Japan Patent Applications, descriptions of current research results in advanced components and cell constructions, and projections of future works.

  15. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  16. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  17. TRANSITION METAL CATALYZED ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  18. COPPER(I)-CATALYZED ATOM TRANSFER RADICAL POLYMERIZATIONS. (R826735)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  19. Oxygen Transfer to Ethylene Catalyzed by the AG(110) Surface

    Science.gov (United States)

    1989-04-01

    Baker Laboratory Cornell University Ithaca, New York 14853, USA +Dedicated to our friend Richard Netter on the occasion of his 70th birthday. Accession...Inc. (especially Mr. Richard Netter ) for financial support. Valuable comments by Professor Robert J. Madix and Maija Zonnevylle are also acknovledged

  20. Mechanistic Study of Oxygen Atom Transfer Catalyzed by Rhenium Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Xiaopeng Shan

    2003-08-05

    Two ionic and one neutral methyl(oxo)rhenium(V) compounds were synthesized and structurally characterized. They were compared in reactivity towards the ligands triphenylphosphane, pyridines, pyridine N-oxides. Assistance from Broensted bases was found on ligand displacement of ionic rhenium compounds as well as nucleophile assistance on oxidation of all compounds. From the kinetic data, crystal structures, and an analysis of the intermediates, a structural formula of PicH{sup +}3{sup -} and mechanisms of ligand displacement and oxidation were proposed.