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Sample records for hydrogen permeable metals

  1. Hydrogen-permeable composite metal membrane and uses thereof

    DOEpatents

    Edlund, David J.; Friesen, Dwayne T.

    1993-06-08

    Various hydrogen production and hydrogen sulfide decomposition processes are disclosed that utilize composite metal membranes that contain an intermetallic diffusion barrier separating a hydrogen-permeable base metal and a hydrogen-permeable coating metal. The barrier is a thermally stable inorganic proton conductor.

  2. Tubular hydrogen permeable metal foil membrane and method of fabrication

    DOEpatents

    Paglieri, Stephen N.; Birdsell, Stephen A.; Barbero, Robert S.; Snow, Ronny C.; Smith, Frank M.

    2006-04-04

    A tubular hydrogen permeable metal membrane and fabrication process comprises obtaining a metal alloy foil having two surfaces, coating the surfaces with a metal or metal alloy catalytic layer to produce a hydrogen permeable metal membrane, sizing the membrane into a sheet with two long edges, wrapping the membrane around an elongated expandable rod with the two long edges aligned and overlapping to facilitate welding of the two together, placing the foil wrapped rod into a surrounding fixture housing with the two aligned and overlapping foil edges accessible through an elongated aperture in the surrounding fixture housing, expanding the elongated expandable rod within the surrounding fixture housing to tighten the foil about the expanded rod, welding the two long overlapping foil edges to one another generating a tubular membrane, and removing the tubular membrane from within the surrounding fixture housing and the expandable rod from with the tubular membrane.

  3. Hydrogen Permeability of Mulitphase V-Ti-Ni Metallic Membranes

    SciTech Connect

    Adams, T. M.; Mickalonis, J.

    2005-10-18

    Development of advanced hydrogen separation membranes in support of hydrogen production processes such as coal gasification and as front end gas purifiers for fuel cell based system is paramount to the successful implementation of a national hydrogen economy. Current generation metallic hydrogen separation membranes are based on Pd-alloys. Although the technology has proven successful, at issue is the high cost of palladium. Evaluation of non-noble metal based dense metallic separation membranes is currently receiving national and international attention. The focal point of the reported work was to evaluate a Group 5A-Ta, Nb, V-based alloy with respect to microstructural features and hydrogen permeability. Electrochemical hydrogen permeation testing of the V-Ti-Ni alloy is reported herein and compared to pure Pd measurements recorded as part of this same study. The V-Ti-Ni was demonstrated to have a steady state hydrogen permeation rate an order of magnitude higher than the pure Pd material in testing conducted at 22 C.

  4. Metal/ceramic composites with high hydrogen permeability

    DOEpatents

    Dorris, Stephen E.; Lee, Tae H.; Balachandran, Uthamalingam

    2003-05-27

    A membrane for separating hydrogen from fluids is provided comprising a sintered homogenous mixture of a ceramic composition and a metal. The metal may be palladium, niobium, tantalum, vanadium, or zirconium or a binary mixture of palladium with another metal such as niobium, silver, tantalum, vanadium, or zirconium.

  5. Permeability of precious metals to hydrogen at 2kb total pressure and elevated temperatures.

    USGS Publications Warehouse

    Chou, I.-Ming

    1986-01-01

    Permeabilities of several commonly used precious metals to hydrogen have been measured at 2kb total pressure and between 450o and 812oC by using the double-capsule oxygen buffer technique.- from Author

  6. Review of hydrogen isotope permeability through materials

    SciTech Connect

    Steward, S.A.

    1983-08-15

    This report is the first part of a comprehensive summary of the literature on hydrogen isotope permeability through materials that do not readily form hydrides. While we mainly focus on pure metals with low permeabilities because of their importance to tritium containment, we also give data on higher-permeability materials such as iron, nickel, steels, and glasses.

  7. Reduced hydrogen permeability at high temperatures

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.; Klopp, W. D.; Misencik, J. A.

    1981-01-01

    CO and CO2 reduce hydrogen loss through iron, nickel, and cobalt based alloy tubes. Method is based on concept that oxide film on metal surface reduces hydrogen permeability through metal; adding CO or CO2 forms oxide films continuously during operation, and hydrogen containment is improved. Innovation enhances prospects for Stirling engine system utilization.

  8. Effect of water on hydrogen permeability

    NASA Technical Reports Server (NTRS)

    Hulligan, David; Tomazic, William A.

    1987-01-01

    Doping of hydrogen with CO and CO2 was developed to reduce hydrogen permeation in Stirling engines by forming a low permeability oxide coating on the inner surface of the heater head tubes. Although doping worked well, under certain circumstances the protective oxide could be chemically reduced by the hydrogen in the engine. Some oxygen is required in the hydrogen to prevent reduction. Eventually, all the oxygen in the hydrogen gas - whatever its source - shows up as water. This is the result of hydrogen reducing the CO, CO2, or the protective inner surface oxides. This water can condense in the engine system under the right conditions. If the concentration of water vapor is reduced to a low enough level, the hydrogen can chemically reduce the oxide coating, resulting in an increase in permeability. This work was done to define the minimum water content required to avoid this reduction in the oxide coating. The results of this testing show that a minimum of approximately 750 ppm water is required to prevent an increase in permeability of CG-27, a high temperature metal alloy selected for Stirling engine heater tubes.

  9. Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    2015-03-01

    Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

  10. System level permeability modeling of porous hydrogen storage materials.

    SciTech Connect

    Kanouff, Michael P.; Dedrick, Daniel E.; Voskuilen, Tyler

    2010-01-01

    A permeability model for hydrogen transport in a porous material is successfully applied to both laboratory-scale and vehicle-scale sodium alanate hydrogen storage systems. The use of a Knudsen number dependent relationship for permeability of the material in conjunction with a constant area fraction channeling model is shown to accurately predict hydrogen flow through the reactors. Generally applicable model parameters were obtained by numerically fitting experimental measurements from reactors of different sizes and aspect ratios. The degree of channeling was experimentally determined from the measurements and found to be 2.08% of total cross-sectional area. Use of this constant area channeling model and the Knudsen dependent Young & Todd permeability model allows for accurate prediction of the hydrogen uptake performance of full-scale sodium alanate and similar metal hydride systems.

  11. Effect of a Nickel-Iron Mixture of Weld Metal on Hydrogen Permeability at Various Temperatures in 316L Stainless Steel

    NASA Astrophysics Data System (ADS)

    Yamazaki, Takahisa; Ikeshoji, Toshi-Taka; Suzumura, Akio; Kobayashi, Daigo; Kamono, Shumpei

    It is important to prevent from hydrogen embrittlement cracking in the heat-affected zone of welded steels. The hydrogen permeation rate for bulk nickel at high temperatures is higher than that of stainless steel, although the reverse is true at low temperatures. Low carbon stainless 316L steel, which contained 12-15% nickel, was selected as the parent material for welding. We have investigated the affect of nickel near the heat-affected zone by measuring the hydrogen permeation at various temperatures. We performed hydrogen permeation tests into the bead on plate specimens using nickel filler. A stationary hydrogen gas flux through the stainless steel specimen was measured by using an orifice and a quadrupole mass spectrometer (QMS). The partial pressure difference for hydrogen that was applied to the specimen was able to be kept constant by maintaining a constant gas flow rate through the orifice in a low- pressure room. An orifice with a 3 mm diameter maintained stationary steady-state hydrogen gas flux from the specimen at 620K, while a 1.2 mm diameter orifice maintained the steady pressure at 520 K. The hydrogen permeability, K was calculated based on the measured steady-state hydrogen gas fluxes at various temperatures. These results plotted as log K versus 1/T (reciprocal temperature) could not be interpolated linearly. The permeability values of the specimen at 570 K and 520 K were less than interpolated ones between the value at 620 K and the value at 520K of the 316 L stainless steel substrate as received.

  12. Determination of hydrogen permeability in commercial and modified superalloys

    NASA Technical Reports Server (NTRS)

    Bhattacharyya, S.; Peterman, W.

    1983-01-01

    The results of hydrogen permeability measurements on several iron- and cobalt-base alloys as well as on two long-ranged ordered alloys over the range of 705 to 870 C (1300 to 1600 F) are summarized. The test alloys included wrought alloys N-155, IN 800, A-286, 19-9DL, and 19-9DL modifications with aluminum, niobium, and misch metal. In addition, XF-818, CRM-6D, SA-F11, and HS-31 were evaluated. Two wrought long-range ordered alloys, Ni3Al and (Fe,Ni)3(V,Al) were also evaluated. All tests were conducted at 20.7 MPa pressure in either pure and/or 1% CO2-doped H2 for test periods as long as 133 h. Detailed analyses were conducted to determine the relative permeability rankings of these alloys and the effect of doping, exit surface oxidation, specimen design variations, and test duration on permeability coefficient, and permeation activation energies were determined. The two long-range ordered alloys had the lowest permeability coefficients in pure H2 when compared with the eight commercial alloys and their modifications. With CO2 doping, significant decrease in permeability was observed in commercial alloys--no doped tests were conducted with the long-range ordered alloys.

  13. Hydrogen interactions with metals

    NASA Technical Reports Server (NTRS)

    Mclellan, R. B.; Harkins, C. G.

    1975-01-01

    Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

  14. Determination of hydrogen permeability in uncoated and coated superalloys

    NASA Technical Reports Server (NTRS)

    Bhattacharyya, S.; Vesely, E. J., Jr.; Hill, V. L.

    1981-01-01

    Hydrogen permeability, diffusivity, and solubility data were obtained for eight wrought and cast high temperature alloys over the range 650 to 815 C. Data were obtained for both uncoated alloys and wrought alloys coated with four commercially available coatings. Activation energies for permeability, diffusivity and solubility were calculated.

  15. The interaction of hydrogen with metal alloys

    NASA Technical Reports Server (NTRS)

    Danford, M. D.; Montano, J. W.

    1991-01-01

    Hydrogen diffusion coefficients were measured for several alloys, and these were determined to be about the same at 25 C for all alloys investigated. The relation of structure, both metallurgical and crystallographic, to the observed hydrogen distribution on charging was investigated, as well as the role of hydride formation in the hydrogen resistance of metal alloys. An attempt was made to correlate the structures and compositions of metal alloys as well as other parameters with the ratios of their notched tensile strengths in hydrogen to that in helium, R(H2/He), which are believed to represent a measure of their hydrogen resistance. Evidence supports the belief that hydrogen permeability and hydrogen resistance are increased by smaller grain sizes for a given alloy composition.

  16. Pathways to metallic hydrogen

    NASA Astrophysics Data System (ADS)

    Silvera, I. F.; Deemyad, S.

    2009-04-01

    The traditional pathway that researchers have used in the goal of producing atomic metallic hydrogen is to compress samples with megabar pressures at low temperature. A number of phases have been observed in solid hydrogen and its isotopes, but all are in the insulating phase. The results of experiment and theory for this pathway are reviewed. In recent years a new pathway has become the focus of this challenge of producing metallic hydrogen, namely a path along the melting line. It has been predicted that the hydrogen melt line will have a peak and with increasing pressure the melt line may descend to zero Kelvin so that high pressure metallic hydrogen may be a quantum liquid. Even at lower pressures hydrogen may melt from a molecular solid to an atomic liquid. Earlier attempts to observe the peak in the melting line were thwarted by diffusion of hydrogen into the pressure cell components and other problems. In the second part of this paper we present a detailed description of our recent successful demonstration of a peak in the melting line of hydrogen.

  17. Stable catalyst layers for hydrogen permeable composite membranes

    DOEpatents

    Way, J. Douglas; Wolden, Colin A

    2014-01-07

    The present invention provides a hydrogen separation membrane based on nanoporous, composite metal carbide or metal sulfide coated membranes capable of high flux and permselectivity for hydrogen without platinum group metals. The present invention is capable of being operated over a broad temperature range, including at elevated temperatures, while maintaining hydrogen selectivity.

  18. Gas Permeable Chemochromic Compositions for Hydrogen Sensing

    NASA Technical Reports Server (NTRS)

    Bokerman, Gary (Inventor); Mohajeri, Nahid (Inventor); Muradov, Nazim (Inventor); Tabatabaie-Raissi, Ali (Inventor)

    2013-01-01

    A (H2) sensor composition includes a gas permeable matrix material intermixed and encapsulating at least one chemochromic pigment. The chemochromic pigment produces a detectable change in color of the overall sensor composition in the presence of H2 gas. The matrix material provides high H2 permeability, which permits fast permeation of H2 gas. In one embodiment, the chemochromic pigment comprises PdO/TiO2. The sensor can be embodied as a two layer structure with the gas permeable matrix material intermixed with the chemochromic pigment in one layer and a second layer which provides a support or overcoat layer.

  19. The hydrogen permeability of Pd{sub 4}S

    SciTech Connect

    O'Brien, Casey; Miller, James; Gellman, Andrew; Morreale, Bryan

    2011-04-01

    Hydrogen permeates rapidly through pure Pd membranes, but H{sub 2}S, a common minor component in hydrogen-containing streams, produces a Pd{sub 4}S film on the Pd surface that severely retards hydrogen permeation. Hydrogen still permeates through the bi-layered Pd{sub 4}S/Pd structure, indicating that the Pd{sub 4}S surface is active for H{sub 2} dissociation; the low hydrogen permeability of the Pd4S film is responsible for the decreased rate of hydrogen transport. In this work, the hydrogen permeability of Pd{sub 4}S was determined experimentally in the 623-773 K temperature range. Bi-layered Pd{sub 4}S/Pd foils were produced by exposing pure Pd foils to H{sub 2}S. H{sub 2} fluxes through the bi-layered Pd{sub 4}S/Pd foils were measured during exposure to both pure H{sub 2} and a 1000 ppm H{sub 2}S in H{sub 2} gas mixture. Our results show that H{sub 2}S slows hydrogen permeation through Pd mainly by producing a Pd{sub 4}S film on the Pd surface that is roughly an order-of-magnitude less permeable to hydrogen (k{sub Pd{sub 4}S} = 10{sup −7.5} exp(−0.22 eV/k{sub B}T) molH{sub 2}/m/s/Pa{sup 1/2}) than pure Pd. The presence of H{sub 2}S in the gas stream results in greater inhibition of hydrogen transport than can be explained by the very low permeability of Pd{sub 4}S. H{sub 2}S may block H2 dissociation sites at the Pd{sub 4}S surface.

  20. Measuring Hydrogen Concentrations in Metals

    NASA Technical Reports Server (NTRS)

    Danford, M. D.

    1985-01-01

    Commercial corrosion-measurement system adapted to electrochemical determination of hydrogen concentrations in metals. New technique based on diffusion of hydrogen through foil specimen of metal. In sample holder, hydrogen produced on one side of foil, either by corrosion reaction or by cathodic current. Hydrogen diffused through foil removed on other side by constant anode potential, which leads to oxidation of hydrogen to water. Anode current is measure of concentration of hydrogen diffusing through foil. System used to study hydrogen uptake, hydrogen elimination by baking, effect of heat treatment, and effect of electroplating on high-strength steels.

  1. Metallization of fluid hydrogen

    SciTech Connect

    Nellis, W.J.; Louis, A.A.; Ashcroft, N.W.

    1997-05-14

    The electrical activity of liquid hydrogen has been measured at the high dynamic pressures, and temperatures that can be achieved with a reverberating shock wave. The resulting data are most naturally interpreted in terms of a continuous transition from a semiconducting to a metallic, largely diatomic fluid, the latter at 140 CPa, (ninefold compression) and 3000 K. While the fluid at these conditions resembles common liquid metals by the scale of its resistivity of 500 micro-ohm-cm, it differs by retaining a strong pairing character, and the precise mechanism by which a metallic state might be attained is still a matter of debate. Some evident possibilities include (i) physics of a largely one-body character, such as a band-overlap transition, (ii) physics of a strong-coupling or many-body character,such as a Mott-Hubbard transition, and (iii) process in which structural changes are paramount.

  2. Structural determinants of the hydrogen peroxide permeability of aquaporins.

    PubMed

    Almasalmeh, Abdulnasser; Krenc, Dawid; Wu, Binghua; Beitz, Eric

    2014-02-01

    Aquaporins (AQP) conduct small, uncharged molecules, such as water (orthodox AQPs), ammonia (aquaammoniaporins) or glycerol (aquaglyceroporins). The physiological functions of AQPs are involved in osmotic volume regulation or the transport of biochemical precursors and metabolic waste products. The recent identification of hydrogen peroxide (H?O?) as a permeant of certain AQPs suggests additional roles in mitigating oxidative stress or enabling paracrine H?O? signalling. Yet, an analysis of the structural requirements of the H?O? permeability of AQPs is missing. We subjected a representative set of wild-type and mutant AQPs to a newly established quantitative phenotypic assay. We confirmed high H?O? permeability of the human aquaammoniaporin AQP8 and found intermediate H?O? permeability of the prototypical orthodox water channel AQP1 from the rat. Differences from an earlier report showing an absence of H?O? permeability of human AQP1 can be explained by expression levels. By generating point mutations in the selectivity filter of rat orthodox aquaporin AQP1, we established a correlation of H?O? permeability primarily with water permeability and secondarily with the pore diameter. Even the narrowest pore of the test set (i.e. rat orthodox aquaporin AQP1 H180F with a pore diameter smaller than that of natural orthodox AQPs) conducted water and H?O?. We further found that H?O? permeability of the aquaglyceroporin from the malaria parasite Plasmodium falciparum was lower despite its wider pore diameter. The data suggest that all water-permeable AQPs are H?O? channels, yet H?O? permeability varies with the isoform. Thus, generally, AQPs must be considered as putative players in situations of oxidative stress (e.g. in Plasmodium-infected red blood cells, immune cells, the cardiovascular system or cells expressing AQP8 in their mitochondria). PMID:24286224

  3. Annealing effect of cermet membranes on hydrogen permeability.

    SciTech Connect

    Song, S.-J.; Wachsman, E. D.; Lee, T. H.; Chen, L.; Dorris, S. E.; Balachandran, U.; Energy Systems; Univ. of Florida

    2006-11-11

    Ni--SrCe{sub 0.8}Yb{sub 0.2}O{sub 3-{delta}} cermet membranes are being developed to separate hydrogen from hydrogen-containing gas mixtures at high temperature. The hydrogen flux of an annealed membrane showed higher flux than that of an as-sintered membrane. The major contribution to overall flux was from ambipolar diffusion through the metal-to-oxide grain boundary. The higher hydrogen permeation flux of an annealed membrane may be understood by its larger metal grains and lower tortuosity, leading to a less-effective length for proton diffusion.

  4. Effect of water on hydrogen permeability. [Stirling engines

    NASA Technical Reports Server (NTRS)

    Hulligan, D. D.; Tomazic, W. A.

    1984-01-01

    Doping of hydrogen with CO or CO2 was developed to reduce hydrogen permeation in Stirling engines by forming low permeability oxide coatings in the heater tubes. An end product of this process is water - which can condense in the cold parts of the engine system. If the water vapor is reduced to a low enough level, the hydrogen can reduce the oxide coating resulting in increased permeability. The equilibrium level of water (oxygen bearing gas) required to avoid reduction of the oxide coating was investigated. Results at 720 C and 13.8 MPa have shown that: (1) pure hydrogen will reduce the coating; (2) 500 ppm CO (500 ppm water equivalent) does not prevent the reduction; and (3) 500 ppm CO2 (1000 ppm water) appears to be close to the equilibrium level. Further tests are planned to define the equilibrium level more precisely and to extend the data to 820 C and 3.4, 6.9, and 13.8 MPa.

  5. Hydrogen environment embrittlement of metals

    NASA Technical Reports Server (NTRS)

    Jewett, R. P.; Walter, R. J.; Chandler, W. T.; Frohmberg, R. P.

    1973-01-01

    Hydrogen environment embrittlement refers to metals stressed while exposed to a hydrogen atmosphere. Tested in air, even after exposure to hydrogen under pressure, this effect is not observed on similar specimens. Much high purity hydrogen is prepared by evaporation of liquid hydrogen, and thus has low levels for potential impurities which could otherwise inhibit or poison the absorbent reactions that are involved. High strength steels and nickel-base allows are rated as showing extreme embrittlement; aluminum alloys and the austenitic stainless steels, as well as copper, have negligible susceptibility to this phenomenon. The cracking that occurs appears to be a surface phenomenon, is unlike that of internal hydrogen embrittlement.

  6. Hydrogen Permeability of Polymer Matrix Composites at Cryogenic Temperatures

    NASA Technical Reports Server (NTRS)

    Grenoble, Ray W.; Gates, Thomas S

    2005-01-01

    This paper presents experimental methods and results of an ongoing study of the correlation between damage state and hydrogen gas permeability of laminated composite materials under mechanical strains and thermal loads. A specimen made from IM-7/977-2 composite material has been mechanically cycled at room temperature to induce microcrack damage. Crack density and tensile modulus were observed as functions of number of cycles. Damage development was found to occur most quickly in the off-axis plies near the outside of the laminate. Permeability measurements were made after 170,000 cycles and 430,000 cycles. Leak rate was found to depend on applied mechanical strain, crack density, and test temperature.

  7. Metal salt catalysts for enhancing hydrogen spillover

    DOEpatents

    Yang, Ralph T; Wang, Yuhe

    2013-04-23

    A composition for hydrogen storage includes a receptor, a hydrogen dissociating metal doped on the receptor, and a metal salt doped on the receptor. The hydrogen dissociating metal is configured to spill over hydrogen to the receptor, and the metal salt is configured to increase a rate of the spill over of the hydrogen to the receptor.

  8. Hydrogen permeation protection for metals

    SciTech Connect

    Tobin, A.G.

    1985-11-26

    A method is proposed to attenuate hydrogen diffusion through fusion reactor components via controlled oxidation of prealloyed surfaces. Alloys of zirconium, vanadium, titanium, niobium, tantalum, tungsten, nickel and iron may be protected from hydrogen isotope permeation by using vanadium as an intermediate layer and either chromium, nickel-chromium, silicon or aluminum as the oxide forming component. This method may also be used to prevent hydrogen embrittlement of metals from external hydrogen environments and is applicable to the majority of alloy systems exhibiting hydrogen embrittlement phenomena.

  9. Effects of hydrogen on metals

    NASA Technical Reports Server (NTRS)

    Cataldo, C. E.

    1969-01-01

    Several rules to guide choice of materials, and methods of welding, electroplating, and heat treatment will provide a method for minimizing failures in storage tanks and related hardware. Failures are caused by high-pressure hydrogen effects, the formation of hydrides in titanium, and hydrogen absorption through various metals processing techniques.

  10. Characterization of tungsten films and their hydrogen permeability

    SciTech Connect

    Nemani?, Vincenc Kova?, Janez; Lungu, Cristian; Porosnicu, Corneliu; Zajec, Bojan

    2014-11-01

    Prediction of tritium migration and its retention within fusion reactors is uncertain due to a significant role of the structural disorder that is formed on the surface layer after plasma exposure. Tungsten films deposited by any of the suitable methods are always disordered and contain a high density of hydrogen traps. Experiments on such films with hydrogen isotopes present a suitable complementary method, which improves the picture of the hydrogen interaction with fusion relevant materials. The authors report on the morphology, composition, and structure of tungsten films deposited by the thermionic vacuum arc method on highly permeable Eurofer substrates. Subsequently, hydrogen permeation studies through these films were carried out in a wide pressure range from 20 to 1000 mbars at 400?C. The final value of the permeation coefficient for four samples after 24?h at 400?C was between P?=?3.2??10{sup ?14}?mol?H{sub 2}/(m?s?Pa{sup 0.5}) and P?=?1.1??10{sup ?15}?mol H{sub 2}/(m s Pa{sup 0.5}). From the time evolution of the permeation flux, it was shown that diffusivity was responsible for the difference in the steady fluxes, as solubility was roughly the same. This is confirmed by XRD data taken on these samples.

  11. Hydrogen permeability degradation of Pd-coated Nb-TiNi alloy caused by its interfacial diffusion

    NASA Astrophysics Data System (ADS)

    Ohtsu, Naofumi; Ishikawa, Kazuhiro; Kobori, Yoshihiro

    2016-01-01

    Pd-coated Nb40Ti30Ni30 (Nb-TiNi) is considered a promising material for hydrogen-permeable membranes because of the low usage of Pd metal. This paper reports the degradation of hydrogen permeability occurring during the permeation experiment above 773 K. Surface analysis using X-ray photoelectron spectroscopy revealed that interdiffusion between the Pd coating and the constituent elements of Nb and Ti progressed during the permeation experiment. The diffused Ti was concentrated near the topmost surface and then formed TiO2, which resulted in a decrease in the Pd concentration at the topmost surface. However, the diffused Nb was observed to bind to Pd in the surface and formed a Pd-Nb alloy beneath the topmost surface. We concluded that these changes caused the decline of the hydrogen permeability at high-temperature conditions.

  12. Electrolytic hydrogen-metal interactions

    SciTech Connect

    McBreen, J.

    1991-01-01

    The electrolyte composition and the electrodic conditions have a major effect on the entry of electrolytic hydrogen into metals. In the case of ferrous metals there is a large body of literature and various promoters have been identified. Only a few inhibitors have been found, such as organic nitriles. This paper reports the complete inhibition of the entry of hydrogen into iron by UPD Zn in concentrated alkali solutions. Less is known about the effect of electrolyte on the entry of hydrogen into palladium. The present work shows that many of the known promoters for ferrous metals actually inhibit the entry and egress of hydrogen from palladium. Permeation results on a Pd membrane in pure 0.1 M NaOH indicate that only 20% of the surface is used for the entry of hydrogen into the metal. In 0.1 M NaOH + 10{sup {minus}3} M NaCN it drops to 5%. The fraction of the surface used strongly depends on electrolyte purity. Impurity effects can account for the discrepant results for electrochemical hydrogen loading of Pd.

  13. Electrolytic hydrogen-metal interactions

    SciTech Connect

    McBreen, J.

    1991-12-31

    The electrolyte composition and the electrodic conditions have a major effect on the entry of electrolytic hydrogen into metals. In the case of ferrous metals there is a large body of literature and various promoters have been identified. Only a few inhibitors have been found, such as organic nitriles. This paper reports the complete inhibition of the entry of hydrogen into iron by UPD Zn in concentrated alkali solutions. Less is known about the effect of electrolyte on the entry of hydrogen into palladium. The present work shows that many of the known promoters for ferrous metals actually inhibit the entry and egress of hydrogen from palladium. Permeation results on a Pd membrane in pure 0.1 M NaOH indicate that only 20% of the surface is used for the entry of hydrogen into the metal. In 0.1 M NaOH + 10{sup {minus}3} M NaCN it drops to 5%. The fraction of the surface used strongly depends on electrolyte purity. Impurity effects can account for the discrepant results for electrochemical hydrogen loading of Pd.

  14. Composite Metal-hydrogen Electrodes for Metal-Hydrogen Batteries

    SciTech Connect

    Ruckman, M W; Wiesmann, H; Strongin, M; Young, K; Fetcenko, M

    1997-04-01

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

  15. Hydrogen Permeability of Incoloy 800H, Inconel 617, and Haynes 230 Alloys

    SciTech Connect

    Pattrick Calderoni

    2010-07-01

    A potential issue in the design of the NGNP reactor and high-temperature components is the permeation of fission generated tritium and hydrogen product from downstream hydrogen generation through high-temperature components. Such permeation can result in the loss of fission-generated tritium to the environment and the potential contamination of the helium coolant by permeation of product hydrogen into the coolant system. The issue will be addressed in the engineering design phase, and requires knowledge of permeation characteristics of the candidate alloys. Of three potential candidates for high-temperature components of the NGNP reactor design, the hydrogen permeability has been documented well only for Incoloy 800H, but at relatively high partial pressures of hydrogen. Hydrogen permeability data have been published for Inconel 617, but only in two literature reports and for partial pressures of hydrogen greater than one atmosphere, far higher than anticipated in the NGNP reactor. The hydrogen permeability of Haynes 230 has not been published. To support engineering design of the NGNP reactor components, the hydrogen permeability of Inconel 617 and Haynes 230 were determined using a measurement system designed and fabricated at the Idaho National Laboratory. The performance of the system was validated using Incoloy 800H as reference material, for which the permeability has been published in several journal articles. The permeability of Incoloy 800H, Inconel 617 and Haynes 230 was measured in the temperature range 650 to 950 C and at hydrogen partial pressures of 10-3 and 10-2 atm, substantially lower pressures than used in the published reports. The measured hydrogen permeability of Incoloy 800H and Inconel 617 were in good agreement with published values obtained at higher partial pressures of hydrogen. The hydrogen permeability of Inconel 617 and Haynes 230 were similar, about 50% greater than for Incoloy 800H and with similar temperature dependence.

  16. Metallic Hydrogen and Nano-Tube Magnets

    NASA Technical Reports Server (NTRS)

    Cole, John W.

    2004-01-01

    When hydrogen is subjected to enough pressure the atoms will be pressed into close enough proximity that each electron is no longer bound to a single proton. The research objectives is to find whether metallic hydrogen can be produced and once produced will the metallic hydrogen be metastable and remain in the metallic form when the pressure is released.

  17. PDTI metal alloy as a hydrogen or hydrocarbon sensitive metal

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W. (Inventor)

    1996-01-01

    A hydrogen sensitive metal alloy contains palladium and titanium to provide a larger change in electrical resistance when exposed to the presence of hydrogen. The alloy can be used for improved hydrogen detection.

  18. Effect of oxide films on hydrogen permeability of candidate Stirling engine heater head tube alloys

    NASA Technical Reports Server (NTRS)

    Schuon, S. R.; Misencik, J. A.

    1981-01-01

    The effect of oxide films developed in situ from CO/CO2 doped hydrogen on high pressure hydrogen permeability at 820 C was studied on N-155, A-286, IN 800, 19-9DL, Nitronic 40, HS-188, and IN 718 tubing in a Stirling materials simulator. The hydrogen permeability decreased with increasing dopant levels of CO or CO2 and corresponding decreases in oxide porosity. Minor reactive alloying elements strongly influenced permeability. At high levels of CO or CO2, a liquid oxide formed on alloys with greater than 50 percent Fe. This caused increased permeability. The oxides formed on the inside tube walls were analyzed and their effective permeabilities were calculated.

  19. Hydrogen Permeability of a Polymer Based Composite Tank Material Under Tetra-Axial Strain

    NASA Technical Reports Server (NTRS)

    Stokes, Eric H.

    2003-01-01

    In order to increase the performance of future expendable and reusable launch vehicles and reduce per-pound payload launch costs, weight reductions have been sought in vehicle components. Historically, the cryogenic propellant tanks for launch vehicles have been constructed from metal. These are some of the largest structural components in the vehicle and contribute significantly to the vehicles total dry weight. A successful replacement material will be conformable, have a high strength to weight ratio, and have a low gas-permeability to the cryogens being stored, i.e., oxygen and hydrogen. Polymer-based composites are likely candidates to fill this role. Polymer and polymer-based composites in general are known to have acceptable gas permeation properties in their as-cured state.1 The use of polymer-based composites for this application has been proposed for some time.2 Some successes have been reported with oxygen3, but other than the DC-XA experience, those with hydrogen have been limited. The primary reason for this has been the small molecular diameter of hydrogen, the lower temperatures of the liquid, and that the composite materials examined to date have all been susceptible to microcrack formation in response to the thermal-mechanical cycles experienced in the use-environment. There have been numerous accounts of composite materials with reported acceptable resistance to the formation of microcracks when exposed to various mechanical and/or thermal cycles. However, virtually all of these studies have employed uniaxial loads and there has been no discussion or empirical evidence pertaining to how these loads relate to the biaxial state of stress in the material in its use environment. Furthermore, many of these studies have suffered from a lack of instrument sensitivity in detecting hydrogen permeability, no standards, insufficient documentation of test conditions, testing of cycled materials in their unload state, and/or false assumptions about the nature of the microcracks in the material. This paper documents the results of hydrogen permeability testing on a Bismaleimide (BMI) based graphite fiber composite material under a variety of tetra-axial strain states.

  20. Method for controlled hydrogen charging of metals

    DOEpatents

    Cheng, Bo-Ching (Fremont, CA); Adamson, Ronald B. (Fremont, CA)

    1984-05-29

    A method for controlling hydrogen charging of hydride forming metals through a window of a superimposed layer of a non-hydriding metal overlying the portion of the hydride forming metals to be charged.

  1. Hydrogen permeability and effect microstructure on mixed protonic-electronic conducting Eu-doped strontium cerate.

    SciTech Connect

    Song, S.-J.; Wachsman, E. D.; Rhodes, J.; Yoon, H.-S.; Zhang, G.; Dorris, S. E.; Balachandran, U.; Energy Technology; Univ. of Florida

    2005-08-01

    The hydrogen permeability of SrCe{sup 0.95}Eu{sup 0.05}O{sup 3-{delta}} was studied as a function of temperature, hydrogen partial pressure (P{sup H2}) gradient, and water vapor partial pressure (P{sup H2O}) gradient. The effect of the microstructure on hydrogen permeability through a 1.72 mm thick membrane was investigated. The ambipolar conductivity calculated from hydrogen permeation fluxes showed the same P{sup O2} and P{sup H2} dependence as the electronic conductivity, for the experimental conditions. The small grained membrane showed higher hydrogen permeability when compared with the larger grained membrane over the entire temperature range investigated.

  2. Interaction Of Hydrogen With Metal Alloys

    NASA Technical Reports Server (NTRS)

    Danford, M. D.; Montano, J. W.

    1993-01-01

    Report describes experiments on interaction of hydrogen with number of metal alloys. Discusses relationship between metallurgical and crystallographic aspects of structures of alloys and observed distributions of hydrogen on charging. Also discusses effect of formation of hydrides on resistances of alloys to hydrogen. Describes attempt to correlate structures and compositions of alloys with their abilities to resist embrittlement by hydrogen.

  3. The effects of fractality on hydrogen permeability across meso-porous membrane

    NASA Astrophysics Data System (ADS)

    Helwani, Z.; Wiheeb, A. D.; Shamsudin, I. K.; Kim, J.; Othman, M. R.

    2015-06-01

    A fractal theory employing a box-counting method was used to describe hydrogen gas diffusion into membrane pores in the meso-porosity regime. The diffusion of the gas into the membrane pore network confirmed the existence of fractal structure in the system. Two fractal identities to represent irregularity and roughness of pore surface and tortuosity of the membrane were obtained and analyzed. Their influences on hydrogen permeability were also evaluated. The fractal permeability model that reflects different hydrogen diffusion mechanisms was calculated and compared with that of the state of the art Kozeny-Carman equation.

  4. The Effect of Carbon Monoxide on the Hydrogen Permeability of a Palladium Membrane

    NASA Astrophysics Data System (ADS)

    Katoh, Masahiro; Nishihara, Katsunori; Kinouchi, Koji; Chohama, Koichi; Horikawa, Toshihide; Tomida, Tahei; Sotowa, Ken-Ichiro

    Plating thin Palladium (Pd) film on the outer surface of a porous stainless steel tube enables very rapid hydrogen permeation with an absolute selectivity. Methane steam reforming for hydrogen production is performed in a Pd membrane reactor. In this reaction, carbon monoxide (CO) synthesized is known to affect hydrogen permeability. The effect on hydrogen permeability and the membrane stability were investigated. After hydrogen was flowed through Pd membrane for 1 hour, CO (1%, 10%, 100% diluted by helium) was flowed on the membrane for 1 hour, and hydrogen was re-permeated through the membrane. Under the all experiment, the temperature, the differential pressure and the flow rate of non-permeation side were 823K, 0.1 MPa and 10 mlmin-1, respectively. After the re-permeating hydrogen, the hydrogen permeation rate increased gradually. Finally the rate arrived at the constant value before CO was flowed. But the necessary time was depend on the concentration of CO. The necessary time for three concentration of CO 1%, 10%, and 100% were 30min, 60min, and 180min, respectively. The reason was that depositing carbon from CO affected to hydrogen permeability. The carbon was changed to methane by hydrogen flow and the membrane was recycled.

  5. Hydrogen permeability through beryllium films and the impact of surface oxides

    NASA Astrophysics Data System (ADS)

    Zajec, Bojan; Nemani?, Vincenc; umer, Marko; Porosnicu, Corneliu; Lungu, Cristian P.

    2013-11-01

    Beryllium will constitute the major part of the first wall of ITER, however, several aspects of the tritium retention and recycling in fusion reactors are still open. Studying details of the hydrogen isotope interactions on Be films is in principle easier and more accurate than on the bulk Be metal since a thin (and therefore more permeable) layer of Be film could be deposited on a desired substrate by applying well controlled methods. Results of the hydrogen permeation through 8 micrometer thick Be films deposited by the thermionic vacuum arc method on Eurofer steel membranes with exposed area of 8.4 cm2 are presented. The permeation reduction factor (PRF) at 400 C varied on six samples from 14 to 135 with respect to the bare Eurofer membrane. The highest PRF value enables expression of the Be film permeability coefficient P by means of a simple model which gives PBe 2 10-15 mol H2/m s Pa0.5. Lower PRF values could be explained by microscopic imperfections which represent parallel hydrogen paths through the Be film and enhance the permeation rate. Some of them were revealed by the SEM while their presence could be confirmed also by observing permeation flux transients recorded after the hydrogen exposure. The two-step process of achieving the steady flux agrees with our numerical simulation. It was found that for unintentionally oxidized samples the extracted regular (eliminated contribution of the pinholes in Be film) permeation rate is almost identical from sample to sample and accounts to j ? 1.2 10-7 H2/m2 s at 1 bar hydrogen driving pressure due to BeO formation. For a non-oxidized sample this value is several times higher, j ? 6.5 10-7 mol H2/m2 s. From the latter follows that PBe ? 1.9 10-14 mol H2/m s Pa0.5, while PBeO 1 10-17 mol H2/m s Pa0.5 can be estimated by assuming a 35 nm thick BeO layer.

  6. Novel Composite Hydrogen-Permeable Membranes for Nonthermal Plasma Reactors for the Decomposition of Hydrogen Sulfide

    SciTech Connect

    Morris Argyle; John Ackerman; Suresh Muknahallipatna; Jerry Hamann; Stanislaw Legowski; Gui-Bing Zhao; Sanil John; Ji-Jun Zhang; Linna Wang

    2007-09-30

    The goal of this experimental project was to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a nonthermal plasma and to recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), but it was not achieved at the moderate pressure conditions used in this study. However, H{sub 2}S was successfully decomposed at energy efficiencies higher than any other reports for the high H{sub 2}S concentration and moderate pressures (corresponding to high reactor throughputs) used in this study.

  7. Novel Metallic Membranes for Hydrogen Separation

    SciTech Connect

    Dogan, Omer

    2011-02-27

    To reduce dependence on oil and emission of greenhouse gases, hydrogen is favored as an energy carrier for the near future. Hydrogen can be converted to electrical energy utilizing fuel cells and turbines. One way to produce hydrogen is to gasify coal which is abundant in the U.S. The coal gasification produces syngas from which hydrogen is then separated. Designing metallic alloys for hydrogen separation membranes which will work in a syngas environment poses significant challenges. In this presentation, a review of technical targets, metallic membrane development activities at NETL and challenges that are facing the development of new technologies will be given.

  8. Hydrogen trapping and the interaction of hydrogen with metals

    NASA Technical Reports Server (NTRS)

    Danford, Merlin D.

    1987-01-01

    A method has been developed for the determination of trapped hydrogen in metal alloys, involving the determination of mobile hydrogen using the electrochemical method and the determination of total hydrogen with the fusion method, the difference in hydrogen concentrations being due to trapped hydrogen. It has been found that hydrogen enters body-centered cubic structures through the grain bodies rather than through the grain boundaries. Hydrogen also diffuses much more rapidly in body-centered cubic structures on charging than in face-centered cubic structures, the hydrogen distribution being more uniform in nature. The energy necessary to cause hydrogen embrittlement is postulated to arise from the changes in crystal lattice energies brought about through interaction of hydrogen with atoms in the metal lattice. The total energy change is more negative for body-centered cubic structures, believed to be the cause of a greater tendency toward hydrogen embrittlement. Finally, the agreement of hydrogen concentrations obtained at 25 C by the electrochemical method with those obtained by the fusion method are taken as a strong indication of the power and validity of the electrochemical method.

  9. METAL HYDRIDE HYDROGEN COMPRESSORS: A REVIEW

    SciTech Connect

    Bowman Jr, Robert C; Yartys, Dr. Volodymyr A.; Lototskyy, Dr. Michael V; Pollet, Dr. B.G.

    2014-01-01

    Metal hydride (MH) thermal sorption compression is an efficient and reliable method allowing a conversion of energy from heat into a compressed hydrogen gas. The most important component of such a thermal engine the metal hydride material itself should possess several material features in order to achieve an efficient performance in the hydrogen compression. Apart from the hydrogen storage characteristics important for every solid H storage material (e.g. gravimetric and volumetric efficiency of H storage, hydrogen sorption kinetics and effective thermal conductivity), the thermodynamics of the metal-hydrogen systems is of primary importance resulting in a temperature dependence of the absorption/desorption pressures). Several specific features should be optimized to govern the performance of the MH-compressors including synchronisation of the pressure plateaus for multi-stage compressors, reduction of slope of the isotherms and hysteresis, increase of cycling stability and life time, together with challenges in system design associated with volume expansion of the metal matrix during the hydrogenation. The present review summarises numerous papers and patent literature dealing with MH hydrogen compression technology. The review considers (a) fundamental aspects of materials development with a focus on structure and phase equilibria in the metal-hydrogen systems suitable for the hydrogen compression; and (b) applied aspects, including their consideration from the applied thermodynamic viewpoint, system design features and performances of the metal hydride compressors and major applications.

  10. A Surface-Modified Hydrogen-Permeable Palladium-Silver Plate

    NASA Astrophysics Data System (ADS)

    Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

    2015-12-01

    A composite target is developed for magnetron sputtering of alloys using silver and palladium with different area ratios. A process is proposed for modification of both surfaces of palladium-silver films formed by PVD and electroplating to improve hydrogen permeability of the amorphous palladium layer electrodeposited from a water solution of its salt at the current density exceeding the diffusion current density for these conditions. The modified palladium-silver membrane becomes hydrogen-permeable at room temperature at the overpressure values up to 0.3 MPa.

  11. Conceptual Launch Vehicles Using Metallic Hydrogen Propellant

    NASA Astrophysics Data System (ADS)

    Cole, John W.; Silvera, Isaac F.; Foote, John P.

    2008-01-01

    Solid molecular hydrogen is predicted to transform into an atomic solid with metallic properties under pressures >4.5 Mbar. Atomic metallic hydrogen is predicted to be metastable, limited by some critical temperature and pressure, and to store very large amounts of energy. Experiments may soon determine the critical temperature, critical pressure, and specific energy availability. It is useful to consider the feasibility of using metastable atomic hydrogen as a rocket propellant. If one assumes that metallic hydrogen is stable at usable temperatures and pressures, and that it can be affordably produced, handled, and stored, then it may be a useful rocket propellant. Assuming further that the available specific energy can be determined from the recombination of the atoms into molecules (216 MJ/kg), then conceptual engines and launch vehicle concepts can be developed. Under these assumptions, metallic hydrogen would be a revolutionary new rocket fuel with a theoretical specific impulse of 1700 s at a chamber pressure of 100 atm. A practical problem that arises is that rocket chamber temperatures may be too high for the use of this pure fuel. This paper examines an engine concept that uses liquid hydrogen or water as a diluent coolant for the metallic hydrogen to reduce the chamber temperature to usable values. Several launch vehicles are then conceptually developed. Results indicate that if metallic hydrogen is experimentally found to have the properties assumed in this analysis, then there are significant benefits. These benefits become more attractive as the chamber temperatures increase.

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

    NASA Technical Reports Server (NTRS)

    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.

  13. Hydrogen transport membranes

    DOEpatents

    Mundschau, Michael V.

    2005-05-31

    Composite hydrogen transport membranes, which are used for extraction of hydrogen from gas mixtures are provided. Methods are described for supporting metals and metal alloys which have high hydrogen permeability, but which are either too thin to be self supporting, too weak to resist differential pressures across the membrane, or which become embrittled by hydrogen. Support materials are chosen to be lattice matched to the metals and metal alloys. Preferred metals with high permeability for hydrogen include vanadium, niobium, tantalum, zirconium, palladium, and alloys thereof. Hydrogen-permeable membranes include those in which the pores of a porous support matrix are blocked by hydrogen-permeable metals and metal alloys, those in which the pores of a porous metal matrix are blocked with materials which make the membrane impervious to gases other than hydrogen, and cermets fabricated by sintering powders of metals with powders of lattice-matched ceramic.

  14. Hydrogen Permeation Through Multilayer Metallic Membranes

    NASA Astrophysics Data System (ADS)

    Andrew, Philip L.

    Hydrogen transport across metal surfaces is pertinent not only to the fueling of a fusion reactor, but also to fusion related technologies such as tritium handling. The rates of these processes and that of hydrogen atoms permeating through the metal bulk were obtained by measuring the steady state permeation rate through polycrystalline metal membranes. The experimental investigation focussed on composite membranes made up of iron, palladium and copper layers. The measurements were made under ultrahigh vacuum conditions using either hydrogen molecules or neutral atoms as the incident species. The mathematical dependence of the steady state permeating flux on the incident flux was used to determine whether hydrogen transport at the vacuum/metal interfaces or within the metal bulk (diffusion) is rate-limiting. The chemical composition of the membrane surfaces, measured by Auger Electron Spectroscopy, was found to have a profound effect on surface-limited permeation. The removal of impurities on an iron surface by Ar ion sputtering was found to increase the magnitude and decrease the temperature dependence of the surface-limited permeation rate constant. Deposition of palladium or iron on sputter-cleaned iron surfaces resulted in a reduction of non-metal surface impurities and a further increase in the rate of surface processes. Application of copper on iron, however, had the opposite effect. This is thought to be due to the slow hydrogen adsorption rates peculiar to group IB metals. A thin copper layer on a palladium membrane had a similar effect: hydrogen transport across that surface was impeded. The results are discussed in terms of practical applications of membranes for pumping or detecting hydrogen. In these schemes it is desired that hydrogen, once dissolved in the metal, preferentially exit on the downstream surface.

  15. On the ground state of metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Chakravarty, S.; Ashcroft, N. W.

    1978-01-01

    A proposed liquid ground state of metallic hydrogen at zero temperature is explored and a variational upper bound to the ground state energy is calculated. The possibility that the metallic hydrogen is a liquid around the metastable point (rs = 1.64) cannot be ruled out. This conclusion crucially hinges on the contribution to the energy arising from the third order in the electron-proton interaction which is shown here to be more significant in the liquid phase than in crystals.

  16. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    PubMed

    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. PMID:25427244

  17. Hydrogen production from methane using oxygen-permeable ceramic membranes

    NASA Astrophysics Data System (ADS)

    Faraji, Sedigheh

    Non-porous ceramic membranes with mixed ionic and electronic conductivity have received significant interest in membrane reactor systems for the conversion of methane and higher hydrocarbons to higher value products like hydrogen. However, hydrogen generation by this method has not yet been commercialized and suffers from low membrane stability, low membrane oxygen flux, high membrane fabrication costs, and high reaction temperature requirements. In this dissertation, hydrogen production from methane on two different types of ceramic membranes (dense SFC and BSCF) has been investigated. The focus of this research was on the effects of different parameters to improve hydrogen production in a membrane reactor. These parameters included operating temperature, type of catalyst, membrane material, membrane thickness, membrane preparation pH, and feed ratio. The role of the membrane in the conversion of methane and the interaction with a Pt/CeZrO2 catalyst has been studied. Pulse studies of reactants and products over physical mixtures of crushed membrane material and catalyst have clearly demonstrated that a synergy exists between the membrane and the catalyst under reaction conditions. The degree of catalyst/membrane interaction strongly impacts the conversion of methane and the catalyst performance. During thermogravimetric analysis, the onset temperature of oxygen release for BSCF was observed to be lower than that for SFC while the amount of oxygen release was significantly greater. Pulse injections of CO2 over crushed membranes at 800C have shown more CO2 dissociation on the BSCF membrane than the SFC membrane, resulting in higher CO formation on the BSCF membrane. Similar to the CO2 pulses, when CO was injected on the samples at 800C, CO2 production was higher on BSCF than SFC. It was found that hydrogen consumption on BSCF particles is 24 times higher than that on SFC particles. Furthermore, Raman spectroscopy and temperature programmed desorption studies of CO and CO2 showed a higher CO and CO2 adsorption (for temperatures ranging from room temperature to 600C) on BSCF compared to the SFC membrane. CO2 reforming reactions on BSCF and SFC dense membranes in a membrane reactor showed higher methane conversion and H2/CO ratio on BSCF than SFC in the presence of the Pt/CeZrO2 catalyst. This high conversion and H2/CO ratio could be ascribed to higher CO, CO2, and H2 adsorption on BSCF than SFC, resulting in higher steam and CO2 reforming on the BSCF. The Pt-Ni/CeZrO2 catalyst exhibits promising performance for hydrogen production. Platinum enhances the reducibility of Ni/Al2O 3 and Ni/CeZrO2 catalysts resulting in improved catalysts for H2 production at moderate temperatures. TPR and Raman studies show an alloy formation in the Pt-Ni/Al2O3 catalyst. Further work is required to study the interaction between Pt and Ni in the bimetallic Pt-Ni/CeZrO2 and Pt-Ni/Al2O3 catalysts. Although the Pt-Ni/Al2O3 catalyst shows high methane conversion in the presence of the BSCF membrane at 800C, the activity of this catalyst is low at 600C. Pt-Ni/CeZrO2 bimetallic catalyst demonstrates superior performance compared to Pt-Ni/Al2O3 catalyst at 600C. The thinner BSCF membrane (2.2 mm) demonstrates a higher methane conversion and H2:CO ratio than the thicker BSCF membrane (2.6 mm) because membrane oxygen flux is inversely proportional to thickness. Varying the pH of the precursor solution during membrane preparation has no significant effect on the oxygen flux or the reaction. The CH 4:CO2 feed ratio significantly affects the hydrogen production over the BSCF membrane. Altering the CH4:CO2 ratio has a direct impact on the oxygen flux, which in turn can influence the reaction pathway. These studies suggest that the Pt-Ni/CeZrO2 catalyst might be suitable for low-temperature hydrocarbon conversion reactions over thin BSCF ceramic membranes. Most importantly, the BSCF membrane can reduce the apparent activation energy of the CO2 reforming reaction by changing the reaction pathway to include more steam reforming.

  18. Computer simulation of hydrogen permeability of structural materials through protective coating defect

    NASA Astrophysics Data System (ADS)

    Kostikova, E. K.; Zaika, Yu V.

    2015-12-01

    In the context of problems of hydrogen and thermonuclear power engineering intensive research of the hydrogen isotopes properties is being conducted. Mathematical models help to specify physical-chemical ideas about the interaction of hydrogen isotopes with structural materials, to estimate the limiting factors and to significantly reduce the expenses of experimental research by means of numerical simulation for different parameters and experimental conditions (including extreme ones). Classical diffusion models are often insufficient. The paper is devoted to the models and numerical solution of the boundary-value problems of hydrogen permeability taking into account nonlinear sorption-desorption dynamics on the surface. Algorithms based on difference approximations. The results of computer simulation of the hydrogen flux from a structural material sample are presented.

  19. Hydrogen storage in metal-organic frameworks.

    PubMed

    Murray, Leslie J; Dinc?, Mircea; Long, Jeffrey R

    2009-05-01

    New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal-organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework-H(2) interactions, and strategies for improving storage capacity (188 references). PMID:19384439

  20. Process for forming a nickel foil with controlled and predetermined permeability to hydrogen

    SciTech Connect

    Engelhaupt, D. E.

    1981-09-22

    The present invention provides a novel process for forming a nickel foil having a controlled and predetermined hydrogen permeability. This process includes the steps of passing a nickel plating bath through a suitable cation exchange resin to provide a purified nickel plating bath free of copper and gold cations, immersing a nickel anode and a suitable cathode in the purified nickel plating bath containing a selected concentration of an organic sulfonic acid such as a napthalene-trisulfonic acid, electrodepositing a nickel layer having the thickness of a foil onto the cathode, and separating the nickel layer from the cathode to provide a nickel foil. The anode is a readilycorrodible nickel anode. The present invention also provides a novel nickel foil having a greater hydrogen permeability than palladium at room temperature.

  1. Impact of Stereospecific Intramolecular Hydrogen Bonding on Cell Permeability and Physicochemical Properties

    PubMed Central

    2014-01-01

    Profiling of eight stereoisomeric T. cruzi growth inhibitors revealed vastly different in vitro properties such as solubility, lipophilicity, pKa, and cell permeability for two sets of four stereoisomers. Using computational chemistry and NMR spectroscopy, we identified the formation of an intramolecular NH?NR3 hydrogen bond in the set of stereoisomers displaying lower solubility, higher lipophilicity, and higher cell permeability. The intramolecular hydrogen bond resulted in a significant pKa difference that accounts for the other structureproperty relationships. Application of this knowledge could be of particular value to maintain the delicate balance of size, solubility, and lipophilicity required for cell penetration and oral administration for chemical probes or therapeutics with properties at, or beyond, Lipinskis rule of 5. PMID:24524242

  2. Process for forming a nickel foil with controlled and predetermined permeability to hydrogen

    DOEpatents

    Engelhaupt, Darell E.

    1981-09-22

    The present invention provides a novel process for forming a nickel foil having a controlled and predetermined hydrogen permeability. This process includes the steps of passing a nickel plating bath through a suitable cation exchange resin to provide a purified nickel plating bath free of copper and gold cations, immersing a nickel anode and a suitable cathode in the purified nickel plating bath containing a selected concentration of an organic sulfonic acid such as a napthalene-trisulfonic acid, electrodepositing a nickel layer having the thickness of a foil onto the cathode, and separating the nickel layer from the cathode to provide a nickel foil. The anode is a readily-corrodible nickel anode. The present invention also provides a novel nickel foil having a greater hydrogen permeability than palladium at room temperature.

  3. Metastable Metal Hydrides for Hydrogen Storage

    DOE PAGESBeta

    Graetz, Jason

    2012-01-01

    The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However, a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however, many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. Onmore » the other hand, the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid, low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However, a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.« less

  4. Final Report: Metal Perhydrides for Hydrogen Storage

    SciTech Connect

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

    2011-07-26

    Hydrogen is a promising energy source for the future economy due to its environmental friendliness. One of the important obstacles for the utilization of hydrogen as a fuel source for applications such as fuel cells is the storage of hydrogen. In the infrastructure of the expected hydrogen economy, hydrogen storage is one of the key enabling technologies. Although hydrogen possesses the highest gravimetric energy content (142 KJ/g) of all fuels, its volumetric energy density (8 MJ/L) is very low. It is desired to increase the volumetric energy density of hydrogen in a system to satisfy various applications. Research on hydrogen storage has been pursed for many years. Various storage technologies, including liquefaction, compression, metal hydride, chemical hydride, and adsorption, have been examined. Liquefaction and high pressure compression are not desired due to concerns related to complicated devices, high energy cost and safety. Metal hydrides and chemical hydrides have high gravimetric and volumetric energy densities but encounter issues because high temperature is required for the release of hydrogen, due to the strong bonding of hydrogen in the compounds. Reversibility of hydrogen loading and unloading is another concern. Adsorption of hydrogen on high surface area sorbents such as activated carbon and organic metal frameworks does not have the reversibility problem. But on the other hand, the weak force (primarily the van der Waals force) between hydrogen and the sorbent yields a very small amount of adsorption capacity at ambient temperature. Significant storage capacity can only be achieved at low temperatures such as 77K. The use of liquid nitrogen in a hydrogen storage system is not practical. Perhydrides are proposed as novel hydrogen storage materials that may overcome barriers slowing advances to a hydrogen fuel economy. In conventional hydrides, e.g. metal hydrides, the number of hydrogen atoms equals the total valence of the metal ions. One LiH molecule contains one hydrogen atom because the valence of a Li ion is +1. One MgH2 molecule contains two hydrogen atoms because the valence of a Mg ion is +2. In metal perhydrides, a molecule could contain more hydrogen atoms than expected based on the metal valance, i.e. LiH1+n and MgH2+n (n is equal to or greater than 1). When n is sufficiently high, there will be plenty of hydrogen storage capacity to meet future requirements. The existence of hydrogen clusters, Hn+ (n = 5, 7, 9, 11, 13, 15) and transition metal ion-hydrogen clusters, M+(H2)n (n = 1-6), such as Sc(H2)n+, Co(H2)n+, etc., have assisted the development of this concept. Clusters are not stable species. However, their existence stimulates our approach on using electric charges to enhance the hydrogen adsorption in a hydrogen storage system in this study. The experimental and modeling work to verify it are reported here. Experimental work included the generation of cold hydrogen plasma through a microwave approach, synthesis of sorbent materials, design and construction of lab devices, and the determination of hydrogen adsorption capacities on various sorbent materials under various electric field potentials and various temperatures. The results consistently show that electric potential enhances the adsorption of hydrogen on sorbents. NiO, MgO, activated carbon, MOF, and MOF and platinum coated activated carbon are some of the materials studied. Enhancements up to a few hundred percents have been found. In general, the enhancement increases with the electrical potential, the pressure applied, and the temperature lowered. Theoretical modeling of the hydrogen adsorption on the sorbents under the electric potential has been investigated with the density functional theory (DFT) approach. It was found that the interaction energy between hydrogen and sorbent is increased remarkably when an electric field is applied. This increase of binding energy offers a potential solution for DOE when looking for a compromise between chemisorption and physisorption for hydrogen storage. Bonding of chemisorption is too strong and requires high temperature for the release of hydrogen. Bonding for the physisorption is too weak for sufficient uptake of hydrogen. Electric field potentials can enhance the physisorption and can be adjusted to yield reversibility required in a system at room temperature.

  5. Optical Signature of Metallization of Hydrogen

    NASA Astrophysics Data System (ADS)

    Cohen, R. E.; Naumov, Ivan; Hemley, Russell J.

    2014-03-01

    All proposed high-pressure structures of hydrogen are based on distorted graphene-structured, honeycomb layers. These give unique signatures for metallization and optical response. Theoretical calculations and an assessment of recent experimental results for dense solid hydrogen lead to a unique scenario for the metallization of hydrogen under pressure. The metallization of hydrogen is very different from that originally proposed via a phase transition to a close-packed monoatomic structure, and different from simple metallization recently used to interpret recent experimental data. These different mechanisms for metallization have very different experimental signatures. We show that the shift of the main visible absorption edge does not constrain the point of band gap closure, in contrast with recent claims. This conclusion is confirmed by measured optical spectra, including spectra obtained to low photon energies in the infrared region for phases III and IV of hydrogen. This work was supported as part of EFree, an Energy Frontier Research Center funded by the US Department of Energy.

  6. Membrane permeable luminescent metal complexes for cellular imaging

    NASA Astrophysics Data System (ADS)

    Neugebauer, Ute; Cosgrave, Lynda; Pellegrin, Yann; Devocelle, Marc; Forster, Robert J.; Keyes, Tia E.

    2012-06-01

    The spectroscopic and photophysical properties of ruthenium polypyridyl polypeptide conjugates of the type [Ru(bpy)2PIC-Argn]n+2+, where bpy is 2,2-bipyridyl (bpy), PIC is 2-(4-carboxyphenyl)imidazo[4,5- f][1,10]phenanthroline and PIC-Argn is this ligand peptide bonded to polyarginine where n is 5 or 8, is described. The resonance Raman spectroscopy of the peptide conjugated complex and parent are strongly pH dependent and demonstrate a switch of lowest energy charge transfer transition between bpy and pic ligands as s function of pH. The pKa of the imidazole ring on the complex is obtained from resonance Raman spectroscopy as 7.8 +/- 0.2. The luminescence lifetime of the complex is strongly oxygen dependent and a Stern-Volmer plot of O2 quenching for [Ru(bpy)2(PIC-Arg8)]10+ yielded a KSV value of 2300 +/- 420 M-1 which was independent of pH over the range 2 to 11. The complexes, because of their large Stokes shifts can, uniquely, be used under identical conditions of probe concentration and excitation wavelength for resonance Raman and luminescence cellular imaging. Cellular imaging was conducted using SP2 myeloma cells which confirmed that the [Ru(bpy)2(PIC-Arg8)]10+ is readily taken up by mammalian cells although the parent and pentarginine analogues are not membrane permeable. Preliminary examples of multi-parameter imaging using these probes were presented. Resonance Raman maps of [Ru(bpy)2(PIC-Arg8)]10+ within living myeloma cells showed on the basis of spectral discrimination, attributed to pH, three distinct regions of the cell could be identified, ascribed to the nucleus, the cytoplasm and the membranes. Luminescence lifetime imaging showed quite large variations in the probe lifetime within the living cell which was tentatively ascribed to variation in O2 concentration about the cell. Preliminary estimates of O2 concentration were made and it was found that the membranes, both inner and outer are the most O2 rich regions of the cell. Overall, we propose that such peptide labeled luminescent metal are potentially a valuable addition to cellular imaging by providing tools for multiplexed analysis of the cell environment.

  7. Abundant Metals Give Precious Hydrogenation Performance

    SciTech Connect

    Bullock, R. Morris

    2013-11-29

    Homogeneous catalysts based on precious (noble) metals have had a profound influence on modern synthetic methods, enabling highly selective synthesis of organic compounds but typically require precious metal catalysts (Ru, Rh, Ir, Pt, and Pd). Increasing efforts have been devoted to the design and discovery of homogeneous catalysts using base metals (e.g., Mn, Fe, Co, Ni, Cu, Mo). Morris et al. report Fe catalysts for asymmetric hydrogenation of C=O bonds. Cobalt catalysts for asymmetric hydrogenation of C=C bonds are described by Chirik et al., and Beller et al. report new nanoscale iron catalysts for synthesis of functionalized anilines through hydrogenation of nitroarenes. The author’s work in this area is supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  8. Noble Metals Would Prevent Hydrogen Embrittlement

    NASA Technical Reports Server (NTRS)

    Paton, N. E.; Frandsen, J. D.

    1987-01-01

    According to proposal, addition of small amounts of noble metals makes iron- and nickel-based alloys less susceptible to embrittlement by hydrogen. Metallurgists demonstrated adding 0.6 to 1.0 percent by weight of Pd or Pt eliminates stress/corrosion cracking in type 4130 steel. Proposal based on assumption that similar levels (0.5 to 1.0 weight percent) of same elements effective against hydrogen embrittlement.

  9. Nanostructures from hydrogen implantation of metals.

    SciTech Connect

    McWatters, Bruce Ray; Causey, Rion A.; DePuit, Ryan J.; Yang, Nancy Y. C.; Ong, Markus D.

    2009-09-01

    This study investigates a pathway to nanoporous structures created by hydrogen implantation in aluminum. Previous experiments for fusion applications have indicated that hydrogen and helium ion implantations are capable of producing bicontinuous nanoporous structures in a variety of metals. This study focuses specifically on hydrogen and helium implantations of aluminum, including complementary experimental results and computational modeling of this system. Experimental results show the evolution of the surface morphology as the hydrogen ion fluence increases from 10{sup 17} cm{sup -2} to 10{sup 18} cm{sup -2}. Implantations of helium at a fluence of 10{sup 18} cm{sup -2} produce porosity on the order of 10 nm. Computational modeling demonstrates the formation of alanes, their desorption, and the resulting etching of aluminum surfaces that likely drives the nanostructures that form in the presence of hydrogen.

  10. Microporous Metal Organic Materials for Hydrogen Storage

    SciTech Connect

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

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

  11. Thermodynamics of hydrogen and vacancies in metals

    NASA Astrophysics Data System (ADS)

    Mao, Juanjuan

    This thesis studies metal-hydrogen systems. The interaction between hydrogen-atoms and vacancies in metals have been elucidated in Fermi-Dirac statistics. Calculations have been presented and compared for specific models in which H-atoms act both as simple interstitial species and form either decorated vacancies or substitutional defects. A model has been presented to explain the superabundant vacancy formation under high hydrogen pressures. The solutions based on these models apply to much lower temperatures and higher concentrations than the traditional ones. These results show abundant vacancies will be formed in the presence of hydrogen; the vacancy concentration is many orders of magnitude larger than those in the H-free lattice. A study of the diffusion of hydrogen in the crack tip area has been provided. The slow diffusivity of H-atoms at low temperatures and the interaction between H-atoms and vacancies in the crack tip plastic zone give an explanation of the experimental data which show a maximum crack growth rate at room temperature. This work is associated with the embrittlement of steel by hydrogen.

  12. Hydrogen peroxide synthesis over metallic catalysts

    NASA Astrophysics Data System (ADS)

    Olivera, P. Paredes; Patrito, E. M.; Sellers, Harrell

    1994-06-01

    The energetics of the elementary reactions involved in the synthesis of hydrogen peroxide over noble metal catalysts have been investigated using the bond order conservation-Morse potential approach (BOC-MP). Enthalpy changes as well as activation energies for forward and reverse reactions were calculated for the different elementary steps which may occur by reaction of H 2 and O 2 on the noble metal series Pd, Pt, Ag and Au. According to the BOC-MP model, under low surface coverage conditions the reaction proceeds along a water channel in which hydroxyl radicals are the main intermediates. No hydrogen peroxide is produced under these conditions. The model indicates that the formation of hydroxyl radicals should be blocked and adsorbed hydroxyls should be destabilized for the reaction to proceed along the hydrogen peroxide channel in which OOH radicals play a fundamental role. In the metal series investigated the production of H 2O 2 is more favorable on gold and silver than on the other metals. Experimental conditions such as hydrogen and oxygen loading of the catalyst are simulated and the role of promoters is discussed.

  13. Critical fields of liquid superconducting metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Jaffe, J.; Ashcroft, N. W.

    1983-01-01

    Liquid metallic hydrogen, in a fully dissociated state, is predicted at certain densities to pass from dirty to clean and from type II to type I superconducting behavior as temperature is lowered. Previously announced in STAR as N82-29374

  14. Method for controlling density and permeability of sintered powdered metals

    NASA Technical Reports Server (NTRS)

    Todd, H. H.

    1968-01-01

    Improved, relatively low-cost method has been developed to produce porous metals with predetermined pore size, pore spacing, and density, utilizing powder-metal processes. The method uses angular not spherical tungsten powder.

  15. Hydrogen Release Studies of Alkali Metal Amidoboranes

    SciTech Connect

    Luedtke, Avery T.; Autrey, Thomas

    2010-04-19

    A series of metal amido boranes LiNH2BH3 (LAB), NaNH2BH3 (SAB), LiNH(Me)BH3 (LMAB), NaNH(Me)BH3 (SMAB), KNH(Me)BH3 (PMAB), and KNH(tBu)BH3 (PBAB) were synthesized, by solution phase methods, and the thermal release of H2 in the solid state was studied. Based on the observed trends in reaction rates of H > Me > tBu and the kinetic isotope effect, the mechanism of hydrogen release from MAB compounds was found to proceed through a bimolecular mechanism involving the intermediacy of a MH (M = Li, Na, or K). The mechanism of hydrogen release from metal amidoboranes, a metal ion assisted hydride transfer, is very different than the mechanism of hydrogen release from the parent compound ammonia borane (AB). The non-volatile products formed from MABs are significantly different than the products formed after hydrogen release from AB. The boron containing resulting from the release of one equivalent of hydrogen from the metal amidoboranes were characterized by MAS 11B NMR spectroscopy and found to contain both BH3 and sp2 hybridized BH groups, consistent with a general structural feature MN(R)=BHN(R)MBH3. This work was funded by the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy as part of the Chemical Hydrogen Storage CoE at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. DOE by Battelle. MAS NMR studies were performed using EMSL, a national scientific user facility sponsored by the Department of Energys Office of Biological and Environmental Research located at PNNL.

  16. Hydrogen isotope permeability through austenitic Cr sbnd Ni steels under neutron irradiation

    NASA Astrophysics Data System (ADS)

    Polosukhin, B. G.; Sulimov, E. M.; Zyrianov, A. P.; Kozlov, A. V.

    1996-10-01

    Experimental data on permeability and diffusion of protium and deuterium through austenitic Cr sbnd Ni steels 18Cr sbnd 10Ni sbnd Ti, 16Cr sbnd 11Ni sbnd 3Mo sbnd Ti and 25Cr sbnd 16Ni sbnd 6Mn sbnd N sbnd V are reported. The data were obtained with special equipment designed and installed at the research reactor IVV-2M. It was shown that parameters of hydrogen isotope transfer in Cr sbnd Ni steels increased substantially during irradiation by fast neutrons of the flux density f < 1.8 10 18 n/m 2s ( E ? 0.1 MeV). Radiation effects increase with a temperature decrease. Thus, at T < 673 K a relative increase of permeability can reach several orders with respect to its value. Deviations isotopic effects from their initial values and other radiation defects were observed.

  17. PERMEABILITY, SOLUBILITY, AND INTERACTION OF HYDROGEN IN POLYMERS- AN ASSESSMENT OF MATERIALS FOR HYDROGEN TRANSPORT

    SciTech Connect

    Kane, M

    2008-02-05

    Fiber-reinforced polymer (FRP) piping has been identified as a leading candidate for use in a transport system for the Hydrogen Economy. Understanding the permeation and leakage of hydrogen through the candidate materials is vital to effective materials system selection or design and development of safe and efficient materials for this application. A survey of the literature showed that little data on hydrogen permeation are available and no mechanistically-based models to quantitatively predict permeation behavior have been developed. However, several qualitative trends in gaseous permeation have been identified and simple calculations have been performed to identify leakage rates for polymers of varying crystallinity. Additionally, no plausible mechanism was found for the degradation of polymeric materials in the presence of pure hydrogen. The absence of anticipated degradation is due to lack of interactions between hydrogen and FRP and very low solubility coefficients of hydrogen in polymeric materials. Recommendations are made to address research and testing needs to support successful materials development and use of FRP materials for hydrogen transport and distribution.

  18. Metallic Hydrogen - Potentially a High Energy Rocket Propellant

    NASA Technical Reports Server (NTRS)

    Cole, John; Silvera, Ike

    2007-01-01

    Pure metallic hydrogen is predicted to have a specific impulse (Isp) of 1700 seconds, but the reaction temperature is too high for current engine materials. Diluting metallic hydrogen with liquid hydrogen can reduce the reaction temperature to levels compatible with current material limits and still provide an Isp greater than 900 s. Metallic hydrogen has not yet been produced on earth, but experimental techniques exist that may change this situation. This paper will provide a brief description of metallic hydrogen and the status of experiments that may soon produce detectable quantities of this material in the lab. Also provided are some characteristics for diluted metallic hydrogen engines and launch vehicles.

  19. Semiempirical, Quantum Mechanical Calculation of Hydrogen Embrittlement in Metals

    NASA Astrophysics Data System (ADS)

    Daw, Murray S.; Baskes, M. I.

    1983-04-01

    A new, semiempirical model of metals and impurities (embedded atom method) makes possible a static treatment of the brittle fracture of a transition metal in the presence of hydrogen. Results indicate that hydrogen can reduce the fracture stress in nickel.

  20. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up 15 wt% of total H2 uptake at 80 bar and 77 K. More importantly, the total H2 uptake by MOF-210 was 2.7 wt% at 80 bar and 298 K, which is the highest number reported for physisorptive materials.

  1. Hydrogen Permeability of Palladium Membrane for Steam-Reforming of Bio-Ethanol Using the Membrane Reactor

    NASA Astrophysics Data System (ADS)

    Kinouchi, Kouji; Katoh, Masahiro; Horikawa, Toshihide; Yoshikawa, Takushi; Wada, Mamoru

    A Palladium membrane was prepared by electro-less plating method on porous stainless steel. The catalytic hydrogen production by steam-reforming of biomass-derived ethanol (bio-ethanol) using a Pd membrane was analyzed by comparing it with those for the reaction using reagent ethanol (the reference sample). And the hydrogen permeability of the palladium membrane was investigated using the same palladium membrane (H2/He selectivity = 249, at ?P = 0.10 MPa, 873 K). As a result, for bio-ethanol, deposited carbon had a negative influence on the hydrogen-permeability of the palladium membrane and hydrogen purity. The sulfur content in the bio-ethanol may have promoted carbon deposition. By using a palladium membrane, it was confirmed that H2 yield (%) was increased. It can be attributed that methane was converted from ethanol and produced more hydrogen by steam reforming, due to the in situ removal of hydrogen from the reaction location.

  2. Powered by DFT: Screening methods that accelerate materials development for hydrogen in metals applications.

    PubMed

    Nicholson, Kelly M; Chandrasekhar, Nita; Sholl, David S

    2014-11-18

    CONSPECTUS: Not only is hydrogen critical for current chemical and refining processes, it is also projected to be an important energy carrier for future green energy systems such as fuel cell vehicles. Scientists have examined light metal hydrides for this purpose, which need to have both good thermodynamic properties and fast charging/discharging kinetics. The properties of hydrogen in metals are also important in the development of membranes for hydrogen purification. In this Account, we highlight our recent work aimed at the large scale screening of metal-based systems with either favorable hydrogen capacities and thermodynamics for hydrogen storage in metal hydrides for use in onboard fuel cell vehicles or promising hydrogen permeabilities relative to pure Pd for hydrogen separation from high temperature mixed gas streams using dense metal membranes. Previously, chemists have found that the metal hydrides need to hit a stability sweet spot: if the compound is too stable, it will not release enough hydrogen under low temperatures; if the compound is too unstable, the reaction may not be reversible under practical conditions. Fortunately, we can use DFT-based methods to assess this stability via prediction of thermodynamic properties, equilibrium reaction pathways, and phase diagrams for candidate metal hydride systems with reasonable accuracy using only proposed crystal structures and compositions as inputs. We have efficiently screened millions of mixtures of pure metals, metal hydrides, and alloys to identify promising reaction schemes via the grand canonical linear programming method. Pure Pd and Pd-based membranes have ideal hydrogen selectivities over other gases but suffer shortcomings such as sensitivity to sulfur poisoning and hydrogen embrittlement. Using a combination of detailed DFT, Monte Carlo techniques, and simplified models, we are able to accurately predict hydrogen permeabilities of metal membranes and screen large libraries of candidate alloys, selections of which are described in this Account. To further increase the number of membrane materials that can be studied with DFT, computational costs need to be reduced either through methods development to break bottlenecks in the performance prediction algorithm, particularly related to transition state identification, or through screening techniques that take advantage of correlations to bypass constraints. PMID:24937509

  3. Hydrogen storage in metal-hydrogen systems and their derivatives

    NASA Astrophysics Data System (ADS)

    Eberle, U.; Arnold, G.; von Helmolt, R.

    During the last years, the power densities of automotive fuel cell systems have been raised dramatically. However, a major technology improvement is still needed for the on-board fuel storage system since hydrogen exhibits a rather low volumetric energy density (regardless whether it is stored as a liquid at cryogenic temperatures or as a compressed gas). Furthermore, the cost for current hydrogen containers is far from what gasoline tanks cost. Therefore, alternatives like solid-state absorbers of hydrogen (e.g. metal hydrides or complex hydrides) are investigated for their feasibility by the car industry. These kinds of systems show very high volumetric storage densities on a materials basis. Unfortunately, the host compounds are usually quite heavy and thus possess a low gravimetric storage density. Also, the thermodynamics and kinetics of the absorption/desorption reactions and their impact on the tank design in general (and on the heat management in particular) have to be considered. Within the framework of this paper, the properties of the most promising solid-state storage systems are discussed and compared to those of the liquid and compressed gaseous hydrogen technologies.

  4. Hydrogen production from simulated hot coke oven gas by using oxygen-permeable ceramics

    SciTech Connect

    Hongwei Cheng; Yuwen Zhang; Xionggang Lu; Weizhong Ding; Qian Li

    2009-01-15

    Hydrogen production from simulated hot coke oven gas (HCOG) was investigated in a BaCo{sub 0.7}Fe{sub 0.2}Nb{sub 0.1}O{sub 3-{delta}} (BCFNO) membrane reactor combined with a Ni/Mg(Al)O catalyst by the partial oxidation with toluene as a model tar compound under atmospheric pressure. The reaction results indicated that toluene was completely converted to H{sub 2} and CO in the catalytic reforming of the simulated HCOG in the temperature range from 825 to 875{sup o}C. Both thermodynamically predicated values and experimental data showed that the selective oxidation of toluene took precedence over that of CH{sub 4} in the reforming reaction. At optimized reaction conditions, the dense oxygen-permeable membrane has an oxygen permeation flux around 12.3 mL cm{sup -2} min{sup -1}, and a CH{sub 4} conversion of 86%, a CO{sub 2} conversion of 99%, a H{sub 2} yield of 88%, and a CO yield of 87% have been achieved. When the toluene and methane were reformed, the amount of H{sub 2} in the reaction effluent gas was about 2 times more than that of original H{sub 2} in simulated HCOG. The results reveal that it is feasible for hydrogen production from HCOG by reforming hydrocarbon compounds in a ceramic oxygen-permeable membrane reactor. 27 refs., 10 figs., 3 abs.

  5. Self-consistent structure of metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.

    1977-01-01

    A calculation is presented of the total energy of metallic hydrogen for a family of face-centered tetragonal lattices carried out within the self-consistent phonon approximation. The energy of proton motion is large and proper inclusion of proton dynamics alters the structural dependence of the total energy, causing isotropic lattices to become favored. For the dynamic lattice the structural dependence of terms of third and higher order in the electron-proton interaction is greatly reduced from static lattice equivalents.

  6. Occludin Content Modulates Hydrogen Peroxide-Induced Increase in Renal Epithelial Paracellular Permeability.

    PubMed

    Janosevic, Danielle; Axis, Josephine; Bacallao, Robert L; Amsler, Kurt

    2016-03-01

    The ability of hydrogen peroxide (H2 O2 ) to increase paracellular permeability of renal epithelial cell monolayers was examined and the role of occludin in this regulation was investigated. H2 O2 treatment increased the paracellular movement of calcein, a marker for the leak pathway permeability, across monolayers of two renal epithelial cell lines, MDCK and LLC-PK1 , in a concentration-dependent manner. At the same concentrations, H2 O2 did not alter transepithelial resistance (TER) nor increase cell death. The magnitude of the H2 O2 -induced increase in leak pathway permeability was inversely related to cellular occludin protein content. H2 O2 treatment did not produce any major change in total cellular content or Triton X-100-soluble or -insoluble fraction content of occludin protein. Occludin protein staining at the tight junction region was diminished following H2 O2 treatment. The most dramatic effect of H2 O2 was on the dynamic mobility of GFP-occludin into the tight junction region. H2 O2 treatment slowed lateral movement of GFP-occludin into the tight junction region but not on the apical membrane. Further, removal of the cytoplasmic C-terminal region of occludin protein eliminated the effect of H2 O2 on GFP-occludin lateral movement into the tight junction region. An increase in the mobile fraction of GFP-occludin was associated with a loss of response to H2 O2 . These data indicate that the H2 O2 -induced increase in renal epithelial cell paracellular permeability is mediated, at least in part, through occludin protein, possibly through a slowing of the rate of occludin movement into the tight junction region. J. Cell. Biochem. 117: 769-779, 2016. © 2015 Wiley Periodicals, Inc. PMID:26348235

  7. Supported Molten Metal Membranes for Hydrogen Separation

    SciTech Connect

    Datta, Ravindra; Ma, Yi Hua; Yen, Pei-Shan; Deveau, Nicholas; Fishtik, Ilie; Mardilovich, Ivan

    2013-09-30

    We describe here our results on the feasibility of a novel dense metal membrane for hydrogen separation: Supported Molten Metal Membrane, or SMMM.1 The goal in this work was to develop these new membranes based on supporting thin films of low-melting, non- precious group metals, e.g., tin (Sn), indium (In), gallium (Ga), or their alloys, to provide a flux and selectivity of hydrogen that rivals the conventional but substantially more expensive palladium (Pd) or Pd alloy membranes, which are susceptible to poisoning by the many species in the coal-derived syngas, and further possess inadequate stability and limited operating temperature range. The novelty of the technology presented numerous challenges during the course of this project, however, mainly in the selection of appropriate supports, and in the fabrication of a stable membrane. While the wetting instability of the SMMM remains an issue, we did develop an adequate understanding of the interaction between molten metal films with porous supports that we were able to find appropriate supports. Thus, our preliminary results indicate that the Ga/SiC SMMM at 550 ºC has a permeance that is an order of magnitude higher than that of Pd, and exceeds the 2015 DOE target. To make practical SMM membranes, however, further improving the stability of the molten metal membrane is the next goal. For this, it is important to better understand the change in molten metal surface tension and contact angle as a function of temperature and gas-phase composition. A thermodynamic theory was, thus, developed, that is not only able to explain this change in the liquid-gas surface tension, but also the change in the solid-liquid surface tension as well as the contact angle. This fundamental understanding has allowed us to determine design characteristics to maintain stability in the face of changing gas composition. These designs are being developed. For further progress, it is also important to understand the nature of solution and permeation process in these molten metal membranes. For this, a comprehensive microkinetic model was developed for hydrogen permeation in dense metal membranes, and tested against data for Pd membrane over a broad range of temperatures.3 It is planned to obtain theoretical and experimental estimates of the parameters to corroborate the model against mental results for SMMM.

  8. Chemical Bonding Forces and Metallization of Hydrogen

    NASA Astrophysics Data System (ADS)

    Naumov, Ivan; Hemley, Russell; Carnegie Inst of Washington Collaboration

    2015-03-01

    Recent theoretical and experimental studies reveal that compressed molecular hydrogen at 200-350 GPa transforms to layered structures consisting of distorted graphene sheets. The new phases of dense solid hydrogen contrast with the long-held view that symmetric close-packed, ambient alkali-metal-like structures form at these high pressures -this raises the question about the nature and fate of molecular bonding in hydrogen on compression. The realization of such unexpected structures can be explained by consideration of simple low-dimensional model systems- H6 rings and graphene-like monolayers. Both molecular quantum chemistry and well-tested solid state approaches show that these model systems like aromatic hydrocarbons exhibit a special stability, associated with the completely filled set of bonding orbitals or valence bands. This close-shell effect persists in progressing to the real layered structures where it prevents the dielectric energy gap from closing, thus delaying the pressure-induced metallization. The latter nevertheless can occur upon further compression via destroying the closed shell electronic structure which is mainly determined by the 1s electrons. The most likely scenario is the lowering of the bonding bands (their bottoms) stemming from the unoccupied atomic 2s and 2p orbitals. This research was supported by EFree, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DESC0001057.

  9. Heavy metal uptake and leaching from polluted soil using permeable barrier in DTPA-assisted phytoextraction.

    PubMed

    Zhao, Shulan; Shen, Zhiping; Duo, Lian

    2015-04-01

    Application of sewage sludge (SS) in agriculture is an alternative technique of disposing this waste. But unreasonable application of SS leads to excessive accumulation of heavy metals in soils. A column experiment was conducted to test the availability of heavy metals to Lolium perenne grown in SS-treated soils following diethylene triamine penta acetic acid (DTPA) application at rates of 0, 10 and 20 mmol kg(-1) soil. In order to prevent metal leaching in DTPA-assisted phytoextraction process, a horizontal permeable barrier was placed below the treated soil, and its effectiveness was also assessed. Results showed that DTPA addition significantly increased metal uptake by L. perenne shoots and metal leaching. Permeable barriers increased metal concentrations in plant shoots and effectively decreased metal leaching from the treated soil. Heavy metals in SS-treated soils could be gradually removed by harvesting L. perenne many times in 1 year and adding low dosage of DTPA days before each harvest. PMID:25354438

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

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac F.; Cole, John W.

    2010-03-01

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

  11. Novel Composite Hydrogen-Permeable Membranes for Non-Thermal Plasma Reactors for the Decomposition of Hydrogen Sulfide

    SciTech Connect

    Morris D. Argyle; John F. Ackerman; Suresh Muknahallipatna; Jerry C. Hamann; Stanislaw Legowski; Guibing Zhao; Sanil John

    2006-09-30

    The goal of this experimental project is to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a non-thermal plasma and recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), although it has yet to be confirmed in this study. Several pulsed corona discharge (PCD) reactors have been fabricated and used to dissociate H{sub 2}S into hydrogen and sulfur. Visual observation shows that the corona is not uniform throughout the reactor. The corona is stronger near the top of the reactor in argon, while nitrogen and mixtures of argon or nitrogen with H{sub 2}S produce stronger coronas near the bottom of the reactor. Both of these effects appear to be explainable base on the different electron collision interactions with monatomic versus polyatomic gases. A series of experiments varying reactor operating parameters, including discharge capacitance, pulse frequency, and discharge voltage were performed while maintaining constant power input to the reactor. At constant reactor power input, low capacitance, high pulse frequency, and high voltage operation appear to provide the highest conversion and the highest energy efficiency for H{sub 2}S decomposition. Reaction rates and energy efficiency per H{sub 2}S molecule increase with increasing flow rate, although overall H{sub 2}S conversion decreases at constant power input. Voltage and current waveform analysis is ongoing to determine the fundamental operating characteristics of the reactors. A metal infiltrated porous ceramic membrane was prepared using vanadium as the metal and an alumina tube. Experiments with this type of membrane are continuing, but the results thus far have been consistent with those obtained in previous project years: plasma driven permeation or superpermeability has not been observed. A new test cell specially designed to test the membranes has been constructed to provide basic science data on superpermeability.

  12. Mechanical properties and permeability of hydrogen isotopes through CrNi35WTiAl alloy, containing radiogenic helium

    SciTech Connect

    Maksimkin, I.P.; Yukhimchuk, A.A.; Boitsov, I.Y.; Malkov, I.L.; Musyaev, R.K.; Baurin, A.Y.; Shevnin, E.V.; Vertey, A.V.

    2015-03-15

    The long-term contact of structural materials (SM) with tritium-containing media makes their properties in terms of kinetic permeability of hydrogen isotopes change. This change is the consequence of the defect formation in SM due to the result of {sup 3}He build-up generated by the radioactive decay of tritium dissolved in SM. This paper presents the experimental results concerning the permeability of hydrogen isotopes through CrNi35WTiAl alloy containing {sup 3}He and the impact of the presence of {sup 3}He and H on its mechanical properties. Tensile tests of cylindrical samples containing various concentrations of {sup 3}He (90, 230 and 560 appm) have been performed in inert and hydrogen atmospheres. The build-up of {sup 3}He has been made using the 'helium trick' technique. The maximal decrease in the plastic characteristics of the CrNi35WTiAl alloy occurs in samples with the highest {sup 3}He (560 appm) content at 873 K. The permeability of deuterium through the CrNi35WTiAl alloy in the initial state and that with 560 appm of {sup 3}He content was explored. The presence of this {sup 3}He concentration has shown an increase in deuterium permeability, evidently due to structural changes in the material under the impact of radiogenic helium.

  13. Ordered pairing in liquid metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Carlsson, A. E.; Ashcroft, N. W.

    1983-01-01

    We study two possible types of pairing involving the protons of a proposed low-temperature liquid phase metallic hydrogen. Electron-proton pairing, which can result in an insulating phase, is investigated by using an approximate solution of an Eliashberg-type equation for the anomalous self-energy. A very low estimate of the transition temperature is obtained by including proton correlations in the effective interaction. For proton-proton pairing, we derive a new proton pair potential based on the Abrikosov wave function. This potential includes the electron-proton interaction to all orders and has a much larger well depth than is obtained with linear screening methods. This suggests the possibility of either a superfluid paired phase analogous to that in He-3, or alternatively a phase with true molecular pairing.

  14. Hydrogen-environment embrittlement of metals: A study

    NASA Technical Reports Server (NTRS)

    Chandler, W. T.; Frohmber, R. P.; Lewett, R. P.; Mcpherson, W. B.; Walter, R. J.

    1973-01-01

    Study includes extensive tests examining effects of hydrogen environment on different high-strength metals and alloys. Recommendations for preventing metal failure include use of hydrogen-resistant coatings and inhibitors. Study includes references to related investigations and discussion of work in progress.

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

    NASA Technical Reports Server (NTRS)

    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.

  16. Novel Composite Hydrogen-Permeable Membranes for Non-Thermal Plasma Reactors for the Decomposition of Hydrogen Sulfide

    SciTech Connect

    Morris D. Argyle; John F. Ackerman; Suresh Muknahallipatna; Jerry C. Hamann; Stanislaw Legowski; Guibling Zhao; Ji-Jun Zhang; Sanil John

    2005-10-01

    The goal of this experimental project is to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a non-thermal plasma and recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), although it has yet to be confirmed in this study. A pulsed corona discharge (PCD) reactor has been fabricated and used to dissociate H{sub 2}S into hydrogen and sulfur. A nonthermal plasma cannot be produced in pure H{sub 2}S with our reactor geometry, even at discharge voltages of up to 30 kV, because of the high dielectric strength of pure H{sub 2}S ({approx}2.9 times higher than air). Therefore, H{sub 2}S was diluted in another gas with lower breakdown voltage (or dielectric strength). Breakdown voltages of H{sub 2}S in four balance gases (Ar, He, N{sub 2} and H{sub 2}) have been measured at different H{sub 2}S concentrations and pressures. Breakdown voltages are proportional to the partial pressure of H{sub 2}S and the balance gas. H{sub 2}S conversion and the reaction energy efficiency depend on the balance gas and H{sub 2}S inlet concentrations. With increasing H{sub 2}S concentrations, H{sub 2}S conversion initially increases, reaches a maximum, and then decreases. H{sub 2}S conversion in atomic balance gases, such as Ar and He, is more efficient than that in diatomic balance gases, such as N{sub 2} and H{sub 2}. These observations can be explained by the proposed reaction mechanism of H{sub 2}S dissociation in different balance gases. The results show that nonthermal plasmas are effective for dissociating H{sub 2}S into hydrogen and sulfur.

  17. Noble metal-free hydrogen evolution catalysts for water splitting.

    PubMed

    Zou, Xiaoxin; Zhang, Yu

    2015-08-01

    Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts. PMID:25886650

  18. Degree of coverage by adsorbed hydrogen atoms of the surface of the passivating film on the metal at a crack tip in corrosion cracking of constructional materials

    SciTech Connect

    Marichev, V.A.

    1985-07-01

    This paper investigates the relationship to potential of the degree of coverage by hydrogen atoms of the surface of passivating films on the metal at a crack tip in the corrosion cracking of constructional materials. The method of determination of this is based on the quantitative concept of the hydrogen permeability alpha of the passivating films at a crack tip in corrosion cracking. The proposed method of determination is one of the consequences of the concept of hydrogen permeability of the passivating layers at a crack tip.

  19. Radiation-induced hydrogen transfer in metals

    NASA Astrophysics Data System (ADS)

    Tyurin, Yu I.; Vlasov, V. A.; Dolgov, A. S.

    2015-11-01

    The paper presents processes of hydrogen (deuterium) diffusion and release from hydrogen-saturated condensed matters in atomic, molecular and ionized states under the influence of the electron beam and X-ray radiation in the pre-threshold region. The dependence is described between the hydrogen isotope release intensity and the current density and the electron beam energy affecting sample, hydrogen concentration in the material volume and time of radiation exposure to the sample. The energy distribution of the emitted positive ions of hydrogen isotopes is investigated herein. Mechanisms of radiation-induced hydrogen transfer in condensed matters are suggested.

  20. NOVEL COMPOSITE HYDROGEN-PERMEABLE MEMBRANES FOR NON-THERMAL PLASMA REACTORS FOR THE DECOMPOSITION OF HYDROGEN SULFIDE

    SciTech Connect

    Morris D. Argyle; John F. Ackerman; Suresh Muknahallipatna; Jerry C. Hamann; Stanislaw Legowski; Ji-Jun Zhang; Guibing Zhao; Robyn J. Alcanzare; Linna Wang; Ovid A. Plumb

    2004-07-01

    The goal of this experimental project is to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a non-thermal plasma and recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), although it has yet to be confirmed in this study. Experiments involving methane conversion reactions were conducted with a preliminary pulsed corona discharge reactor design in order to test and improve the reactor and membrane designs using a non-toxic reactant. This report details the direct methane conversion experiments to produce hydrogen, acetylene, and higher hydrocarbons utilizing a co-axial cylinder (CAC) corona discharge reactor, pulsed with a thyratron switch. The reactor was designed to accommodate relatively high flow rates (655 x 10{sup -6} m{sup 3}/s) representing a pilot scale easily converted to commercial scale. Parameters expected to influence methane conversion including pulse frequency, charge voltage, capacitance, residence time, and electrode material were investigated. Conversion, selectivity and energy consumption were measured or estimated. C{sub 2} and C{sub 3} hydrocarbon products were analyzed with a residual gas analyzer (RGA). In order to obtain quantitative results, the complex sample spectra were de-convoluted via a linear least squares method. Methane conversion as high as 51% was achieved. The products are typically 50%-60% acetylene, 20% propane, 10% ethane and ethylene, and 5% propylene. First Law thermodynamic energy efficiencies for the system (electrical and reactor) were estimated to range from 38% to 6%, with the highest efficiencies occurring at short residence time and low power input (low specific energy) where conversion is the lowest (less than 5%). The highest methane conversion of 51% occurred at a residence time of 18.8 s with a flow rate of 39.4 x 10{sup -6} m{sup 3}/s (5 ft{sup 3}/h) and a specific energy of 13,000 J/l using niobium and platinum coated stainless steel tubes as cathodes. Under these conditions, the First Law efficiency for the system was 8%. Under similar reaction conditions, methane conversions were {approx}50% higher with niobium and platinum coated stainless steel cathodes than with a stainless steel cathode.

  1. Thermochemical Ablation Therapy of VX2 Tumor Using a Permeable Oil-Packed Liquid Alkali Metal

    PubMed Central

    Guo, Ziyi; Zhang, Qiang

    2015-01-01

    Objective Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors. Methods Permeable oil-packed sodiumpotassium (NaK) was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluated using the Fluke Ti400 Thermal Imager. The thermochemical effect of the NaK-oil mixture on VX2 tumors was evaluated by performing perfusion CT scans both before and after treatment in 10 VX2 rabbit model tumors. VX2 tumors were harvested from two rabbits immediately after treatment to assess their viability using trypan blue and hematoxylin and eosin (H.E.) staining. Results The injection of the NaKoil mixture resulted in significantly higher heat in the ablation areas. The permeable oil controlled the rate of heat released during the NaK reaction with water in the living tissue. Perfusion computed tomography and its parameter map confirmed that the NaKoil mixture had curative effects on VX2 tumors. Both trypan blue and H.E. staining showed partial necrosis of the VX2 tumors. Conclusions The NaKoil mixture may be used successfully to ablate tumor tissue in vivo. With reference to the controlled thermal and chemical lethal injury to tumors, using a liquid alkali in ablation is potentially an effective and safe method to treat malignant tumors. PMID:25885926

  2. Hydrogen Embrittlement of Metals: Atomic hydrogen from a variety of sources reduces the ductility of many metals.

    PubMed

    Rogers, H C

    1968-03-01

    Hydrogen interacts with many metals to reduce their ductility (2) and frequently their strength also. It enters metals in the atomic form, diffusing very rapidly even at normal temperatures. During melting and fabrication, as well as during use, there are various ways in which metals come in contact with hydrogen and absorb it. The absorbed hydrogen may react irreversibly with oxides or carbides in some metals to produce a permanently degraded structure. It may also recombine at internal surfaces of defects of various types to form gaseous molecular hydrogen under pressures sufficiently high to form metal blisters when the recombination occurs near the outer surface. In other metals, brittle hydrides that lower the mechanical properties of the metal are formed. Another type of embrittlement is reversible, depending on the presence of hydrogen in the metal lattice during deformation for its occurrence. Under some conditions the failure may be delayed for long periods. A number of different mechanisms have been postulated to explain reversible embrittlement. According to some theories hydrogen interferes with the processes of plastic deformation in metals, while according to others it enhances the tendency for cracking. PMID:17775040

  3. Effects of high pressure hydrogen on metals

    NASA Technical Reports Server (NTRS)

    Chandler, W. T.; Walter, R. J.

    1970-01-01

    Hydrogen environment embrittlement causes failure of hydrogen storage vessels at and below design pressures of 5000 to 6000 psi. Investigation of thirty-five alloys determines their susceptibility to such embrittlement.

  4. Determination of the Darcy permeability of porous media including sintered metal plugs

    NASA Technical Reports Server (NTRS)

    Frederking, T. H. K.; Hepler, W. A.; Yuan, S. W. K.; Feng, W. F.

    1986-01-01

    Sintered-metal porous plugs with a normal size of the order of 1-10 microns are used to evaluate the Darcy permeability of laminar flow at very small velocities in laminar fluids. Porous media experiment results and data adduced from the literature are noted to support the Darcy law analog for normal fluid convection in the laminar regime. Low temperature results suggest the importance of collecting room temperature data prior to runs at liquid He(4) temperatures. The characteristic length diagram gives a useful picture of the tolerance range encountered with a particular class of porous media.

  5. Metal Dichalcogenides Monolayers: Novel Catalysts for Electrochemical Hydrogen Production

    PubMed Central

    Pan, Hui

    2014-01-01

    Catalyst-driven electrolysis of water is considered as a “cleanest” way for hydrogen production. Finding cheap and abundant catalysts is critical to the large-scale implementation of the technology. Two-dimensional metal dichalcogenides nanostructures have attracted increasing attention because of their catalytic performances in water electrolysis. In this work, we systematically investigate the hydrogen evolution reduction of metal dichalcogenides monolayers based on density-functional-theory calculations. We find that metal disulfide monolayers show better catalytic performance on hydrogen production than other metal dichalcogenides. We show that their hydrogen evolution reduction strongly depends on the hydrogen coverage and the catalytic performance reduces with the increment of coverage because of hydrogenation-induced lower conductivity. We further show that the catalytic performance of vanadium disulfide monolayer is comparable to that of Pt at lower hydrogen coverage and the performance at higher coverage can be improved by hybridizing with conducting nanomaterials to enhance conductivity. These metal disulfide monolayers with lower overpotentials may apply to water electrolysis for hydrogen production. PMID:24967679

  6. Metal Dichalcogenides Monolayers: Novel Catalysts for Electrochemical Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Pan, Hui

    2014-06-01

    Catalyst-driven electrolysis of water is considered as a ``cleanest'' way for hydrogen production. Finding cheap and abundant catalysts is critical to the large-scale implementation of the technology. Two-dimensional metal dichalcogenides nanostructures have attracted increasing attention because of their catalytic performances in water electrolysis. In this work, we systematically investigate the hydrogen evolution reduction of metal dichalcogenides monolayers based on density-functional-theory calculations. We find that metal disulfide monolayers show better catalytic performance on hydrogen production than other metal dichalcogenides. We show that their hydrogen evolution reduction strongly depends on the hydrogen coverage and the catalytic performance reduces with the increment of coverage because of hydrogenation-induced lower conductivity. We further show that the catalytic performance of vanadium disulfide monolayer is comparable to that of Pt at lower hydrogen coverage and the performance at higher coverage can be improved by hybridizing with conducting nanomaterials to enhance conductivity. These metal disulfide monolayers with lower overpotentials may apply to water electrolysis for hydrogen production.

  7. Disposal pathway for tritiated reactive metals and tritiated hydrogen gas

    SciTech Connect

    Antoniazzi, A. B.; Morton, C. S.

    2008-07-15

    Kinectrics and its predecessor company Ontario Hydro Research Div. (a division of Ontario Hydro) had a fully operational tritium laboratory on site since the early 1980's. During those years numerous projects and experiments were undertaken using hydrogen and tritium for the most part. Metals with an affinity for hydrogen are commonly employed as scavengers of hydrogenic gases from process streams or as hydrogen storage mediums. The two most common of these metals used were depleted uranium and a zirconium-iron alloy (SAES St198). The break-up of Ontario Hydro through deregulation activities resulted in the building of a new, smaller, tritium laboratory and the decommissioning of the original tritium laboratory. Decommissioning activities resulted in the need to safely dispose of these reactive metals. Disposal of these metals is not straight forward. For safe, long term, disposal it has been decided to oxidize the metals in a controlled fashion. The oxidized beds, containing the metals, will be sent to a radioactive waste site for long term storage. Options for disposal of tritiated hydrogen gas are presented and discussed. This paper provides a disposal pathway for tritiated reactive metals and hydrogen thereby closing the loop in tritium handling. (authors)

  8. Hydrogen evolution by a metal-free electrocatalyst.

    PubMed

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Du, Aijun; Jaroniec, Mietek; Qiao, Shi Zhang

    2014-01-01

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics. PMID:24769657

  9. Hydrogen evolution by a metal-free electrocatalyst

    NASA Astrophysics Data System (ADS)

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Du, Aijun; Jaroniec, Mietek; Qiao, Shi Zhang

    2014-04-01

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

  10. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    SciTech Connect

    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.

  11. Hydrogen sensors based on catalytic metals

    NASA Astrophysics Data System (ADS)

    Beklemyshev, V. I.; Berezine, V.; Bykov, Victor A.; Kiselev, L.; Makhonin, I.; Pevgov, V.; Pustovoy, V.; Semynov, A.; Sencov, Y.; Shkuropat, I.; Shokin, A.

    1999-11-01

    On the base of microelectronical and micromechanical technology were designed and developed converters of hydrogen concentration to electrical signals. The devices of controlling concentration of hydrogen in the air were developed. These devices were applied for ensuring fire and explosion security of complex technological teste of missile oxygen-hydrogen engine, developed for cryogenic accelerations block. The sensor block of such device was installed directly on the armor-plate, to which was attached tested engine.

  12. Hydrogen separation membrane on a porous substrate

    DOEpatents

    Song, Sun-Ju (Orland Park, IL); Lee, Tae H. (Naperville, IL); Chen, Ling (Woodridge, IL); Dorris, Stephen E. (LaGrange Park, IL); Balachandran, Uthamalingam (Hinsdale, IL)

    2011-06-14

    A hydrogen permeable membrane is disclosed. The membrane is prepared by forming a mixture of metal oxide powder and ceramic oxide powder and a pore former into an article. The article is dried at elevated temperatures and then sintered in a reducing atmosphere to provide a dense hydrogen permeable portion near the surface of the sintered mixture. The dense hydrogen permeable portion has a higher initial concentration of metal than the remainder of the sintered mixture and is present in the range of from about 20 to about 80 percent by volume of the dense hydrogen permeable portion.

  13. Exploring metal hydrides using autoclave and multi-anvil hydrogenations

    NASA Astrophysics Data System (ADS)

    Puhakainen, Kati

    Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) , b = 9.719(2) , and c = 4.4764(8) . Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) . Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62 entities with the lattice parameters of 7.8425(9) and 8.1572(4) , respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment.

  14. Interactions of hydrogen isotopes and oxides with metal tubes

    SciTech Connect

    Longhurst, G. R.; Cleaver, J.

    2008-07-15

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

  15. Interactions of Hydrogen Isotopes and Oxides with Metal Tubes

    SciTech Connect

    Glen R. Longhurst

    2008-08-01

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

  16. Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation.

    PubMed

    Primo, Ana; Neatu, Florentina; Florea, Mihaela; Parvulescu, Vasile; Garcia, Hermenegildo

    2014-01-01

    Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene. PMID:25342228

  17. Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation

    NASA Astrophysics Data System (ADS)

    Primo, Ana; Neatu, Florentina; Florea, Mihaela; Parvulescu, Vasile; Garcia, Hermenegildo

    2014-10-01

    Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene.

  18. Ordered ground states of metallic hydrogen and deuterium

    NASA Technical Reports Server (NTRS)

    Ashcroft, N. W.

    1981-01-01

    The physical attributes of some of the more physically distinct ordered states of metallic hydrogen and metallic deuterium at T = 0 and nearby are discussed. The likelihood of superconductivity in both is considered with respect to the usual coupling via the density fluctuations of the ions.

  19. Heat-actuated metal hydride hydrogen compressor testing

    SciTech Connect

    Piraino, M.; Metz, P.D.; Nienke, J.L.; Freitelberg, A.S.; Rahaman, R.S.

    1985-09-01

    Electric utilities use hydrogen for cooling turbine generators. The majority of the utilities purchase the gas from industrial gas markets. On-site electrolytic hydrogen production may prove advantageous both logistically and economically. In order to demonstrate this concept, Public Service Electric and Gas Co. (PSE and G) and EPRI installed an electrolyzer at the Sewaren (NJ) station. To compress the gas, PSE and G purchased a heat-activated metal hydride compressor from Ergenics, Inc. This report describes closed- and open-cycle tests conducted on this metal hydride hydrogen compressor. Test systems, plans, methodologies, and results are presented. A brief discussion evaluates these performance results, addresses some of the practical problems involved with electrolyzer-compressor interface, and compares the costs and benefits of metal hydride versus mechanical hydrogen compression for utility generator cooling.

  20. DEVELOPMENT OF A NON-NOBLE METAL HYDROGEN PURIFICATION SYSTEM

    SciTech Connect

    Korinko, P; Kyle Brinkman, K; Thad Adams, T; George Rawls, G

    2008-11-25

    Development of advanced hydrogen separation membranes in support of hydrogen production processes such as coal gasification and as front end gas purifiers for fuel cell based system is paramount to the successful implementation of a national hydrogen economy. Current generation metallic hydrogen separation membranes are based on Pd-alloys. Although the technology has proven successful, at issue is the high cost of palladium. Evaluation of non-noble metal based dense metallic separation membranes is currently receiving national and international attention. The focus of the reported work was to develop a scaled reactor with a VNi-Ti alloy membrane to replace a production Pd-alloy tube-type purification/diffuser system.

  1. Production of negative hydrogen ions on metal grids

    SciTech Connect

    Oohara, W.; Maetani, Y.; Takeda, Takashi; Takeda, Toshiaki; Yokoyama, H.; Kawata, K.

    2015-03-15

    Negative hydrogen ions are produced on a nickel grid with positive-ion irradiation. In order to investigate the production mechanism, a copper grid without the chemisorption of hydrogen atoms and positive helium ions without negative ionization are used for comparison. Positive hydrogen ions reflected on the metal surface obtain two electrons from the surface and become negatively ionized. It is found that the production yield of negative ions by desorption ionization of chemisorbed hydrogen atoms seems to be small, and the production is a minor mechanism.

  2. Influence of gaseous hydrogen on metals

    NASA Technical Reports Server (NTRS)

    Walter, R. J.; Chandler, W. T.

    1973-01-01

    Tensile, fracture toughness, threshold stress intensity for sustained-load crack growth, and cyclic and sustained load crack growth rate measurements were performed on a number of alloys in high-pressure hydrogen and helium environments. The results of tensile tests performed in 34.5 MN/m2 (5000 psi) hydrogen indicated that Inconel 625 was considerable embrittled at ambient temperature but was not embrittled at 144 K (-200 F). The tensile properties of AISI 321 stainless steel were slightly reduced at ambient temperature and 144 K (-200 F). The tensile properties of Ti-5Al-2.5 Sn ELI were essentially unaffected by hydrogen at 144 K (-200 F). OFHC copper was not embrittled by hydrogen at ambient temperature or at 144 K (-200 F).

  3. Critical behavior in the hydrogen insulator-metal transition

    NASA Technical Reports Server (NTRS)

    Hemley, R. J.; Mao, H. K.

    1990-01-01

    The vibrational Raman spectrum of solid hydrogen has been measured from 77 to 295 K in the vicinity of the recently observed insulator-metal transition and low-temperature phase transition at 150 gigapascals. The measurements provide evidence for a critical point in the pressure-temperature phase boundary of the low-temperature transition. The result suggests that below the critical temperature the insulator-metal transition changes from continuous to discontinuous, consistent with the general criteria originally proposed by Mott (1949) for metallization by band-gap closure. The effect of temperature on hydrogen metallization closely resembles that of the lower-pressure insulator-metal transitions in doped V2O3 alloys.

  4. Membrane for hydrogen recovery from streams containing hydrogen sulfide

    DOEpatents

    Agarwal, Pradeep K.

    2007-01-16

    A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

  5. Hydrogen evolution from water through metal sulfide reactions

    NASA Astrophysics Data System (ADS)

    Saha, Arjun; Raghavachari, Krishnan

    2013-11-01

    Transition metal sulfides play an important catalytic role in many chemical reactions. In this work, we have conducted a careful computational study of the structures, electronic states, and reactivity of metal sulfide cluster anions M2SX- (M = Mo and W, X = 4-6) using density functional theory. Detailed structural analysis shows that these metal sulfide anions have ground state isomers with two bridging sulfide bonds, notably different in some cases from the corresponding oxides with the same stoichiometry. The chemical reactivity of these metal sulfide anions with water has also been carried out. After a thorough search on the reactive potential energy surface, we propose several competitive, energetically favorable, reaction pathways that lead to the evolution of hydrogen. Selectivity in the initial water addition and subsequent hydrogen migration are found to be the key steps in all the proposed reaction channels. Initial adsorption of water is most favored involving a terminal metal sulfur bond in Mo2S4- isomers whereas the most preferred orientation for water addition involves a bridging metal sulfur bond in the case of W2S4- and M2S5- isomers. In all the lowest energy H2 elimination steps, the interacting hydrogen atoms involve a metal hydride and a metal hydroxide (or thiol) group. We have also observed a higher energy reaction channel where the interacting hydrogen atoms in the H2 elimination step involve a thiol (-SH) and a hydroxyl (-OH) group. For all the reaction pathways, the Mo sulfide reactions involve a higher barrier than the corresponding W analogues. We observe for both metals that reactions of M2S4- and M2S5- clusters with water to liberate H2 are exothermic and involve modest free energy barriers. However, the reaction of water with M2S6- is highly endothermic with a considerable barrier due to saturation of the local bonding environment.

  6. A statistical model of hydrogen-induced fracture of metals

    NASA Astrophysics Data System (ADS)

    Indeitsev, D. A.; Osipova, E. V.; Polyanskiy, V. A.

    2014-11-01

    The fracture process of metals due to hydrogen embrittlement is described theoretically as a first-order phase transition. The fractured and unfractured phases are in equilibrium at the instant of fracture and are described by the equality of stresses and thermodynamic potentials. In the context of this approach, the dependences of the fracture stress on the molar hydrogen concentration and on the fracture deformation are calculated. The dependence on the molar hydrogen concentration turned out to be close to the power dependence, while the dependence on the fracture deformation is very close to linear. Not only the qualitative but also the quantitative correspondence of this model to the experimental results is shown.

  7. Selectivity in nitrile hydrogenation catalyzed by group VII metals

    SciTech Connect

    Dobrotvorskii, A.M.; Yakushkin, M.I.; Smaeva, T.P.

    1987-10-20

    The catalytic hydrogenation of nitriles of synthetic fatty acids is one of the methods of preparing higher primary aliphatic amines. This work is devoted to an analysis of the factors which affect the selectivity of this process in the direction of obtaining primary amines and which are connected primarily with the strength of adsorption of intermediate reaction products on transition metals. The hydrogenation of capronitrile was selected as a model. To study the effect of the nature of metallic catalysts on their activity and selectivity, we prepared and tested the following catalysts: nickel, cobalt, rhodium, osmium, platinum, and palladium, supported on industrial ..gamma..-aluminum oxide. Characteristics of the catalysts tested are given.

  8. Optical hydrogen sensors based on metal-hydrides

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

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

    NASA Technical Reports Server (NTRS)

    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.

  10. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1990-08-28

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

  11. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A. (Richland, WA); Hallen, Richard T. (Richland, WA)

    1990-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

  12. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1991-10-15

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

  13. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A. (Richland, WA); Hallen, Richard T. (Richland, WA)

    1991-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

  14. Structural tailoring of hydrogen-bonded poly(acrylic acid)/poly(ethylene oxide) multilayer thin films for reduced gas permeability.

    PubMed

    Xiang, Fangming; Ward, Sarah M; Givens, Tara M; Grunlan, Jaime C

    2015-02-01

    Hydrogen bonded poly(acrylic acid) (PAA)/poly(ethylene oxide) (PEO) layer-by-layer assemblies are highly elastomeric, but more permeable than ionically bonded thin films. In order to expand the use of hydrogen-bonded assemblies to applications that require a better gas barrier, the effect of assembling pH on the oxygen permeability of PAA/PEO multilayer thin films was investigated. Altering the assembling pH leads to significant changes in phase morphology and bonding. The amount of intermolecular hydrogen bonding between PAA and PEO is found to increase with increasing pH due to reduction of COOH dimers between PAA chains. This improved bonding leads to smaller PEO domains and lower gas permeability. Further increasing the pH beyond 2.75 results in higher oxygen permeability due to partial deprotonation of PAA. By setting the assembling pH at 2.75, the negative impacts of COOH dimer formation and PAA ionization on intermolecular hydrogen bonding can be minimized, leading to a 50% reduction in the oxygen permeability of the PAA/PEO thin film. A 20 bilayer coating reduces the oxygen transmission rate of a 1.58 mm natural rubber substrate by 20 ×. These unique nanocoatings provide the opportunity to impart a gas barrier to elastomeric substrates without altering their mechanical behavior. PMID:25519816

  15. HYDROGEN EMBRITTLEMENT OF METALS: A PRIMER FOR THE FAILURE ANALYST

    SciTech Connect

    Louthan, M

    2008-01-31

    Hydrogen reduces the service life of many metallic components. Such reductions may be manifested as blisters, as a decrease in fatigue resistance, as enhanced creep, as the precipitation of a hydride phase and, most commonly, as unexpected, macroscopically brittle failure. This unexpected, brittle fracture is commonly termed hydrogen embrittlement. Frequently, hydrogen embrittlement occurs after the component has been is service for a period of time and much of the resulting fracture surface is distinctly intergranular. Many failures, particularly of high strength steels, are attributed to hydrogen embrittlement simply because the failure analyst sees intergranular fracture in a component that served adequately for a significant period of time. Unfortunately, simply determining that a failure is due to hydrogen embrittlement or some other form of hydrogen induced damage is of no particular help to the customer unless that determination is coupled with recommendations that provide pathways to avoid such damage in future applications. This paper presents qualitative and phenomenological descriptions of the hydrogen damage processes and outlines several metallurgical recommendations that may help reduce the susceptibility of a particular component or system to the various forms of hydrogen damage.

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

    SciTech Connect

    Way, J.; Wolden, Colin

    2013-09-30

    Colorado School of Mines (CSM) developed high temperature, hydrogen permeable membranes that contain no platinum group metals with the goal of separating hydrogen from gas mixtures representative of gasification of carbon feedstocks such as coal or biomass in order to meet DOE NETL 2015 hydrogen membrane performance targets. We employed a dual synthesis strategy centered on transition metal carbides. In the first approach, novel, high temperature, surface diffusion membranes based on nanoporous Mo{sub 2}C were fabricated on ceramic supports. These were produced in a two step process that consisted of molybdenum oxide deposition followed by thermal carburization. Our best Mo{sub 2}C surface diffusion membrane achieved a pure hydrogen flux of 367 SCFH/ft{sup 2} at a feed pressure of only 20 psig. The highest H{sub 2}/N{sub 2} selectivity obtained with this approach was 4.9. A transport model using “dusty gas” theory was derived to describe the hydrogen transport in the Mo{sub 2}C coated, surface diffusion membranes. The second class of membranes developed were dense metal foils of BCC metals such as vanadium coated with thin (< 60 nm) Mo{sub 2}C catalyst layers. We have fabricated a Mo{sub 2}C/V composite membrane that in pure gas testing delivered a H{sub 2} flux of 238 SCFH/ft{sup 2} at 600 °C and 100 psig, with no detectable He permeance. This exceeds the 2010 DOE Target flux. This flux is 2.8 times that of pure Pd at the same membrane thickness and test conditions and over 79% of the 2015 flux target. In mixed gas testing we achieved a permeate purity of ≥99.99%, satisfying the permeate purity milestone, but the hydrogen permeance was low, ~0.2 SCFH/ft{sup 2}.psi. However, during testing of a Mo{sub 2}C coated Pd alloy membrane with DOE 1 feed gas mixture a hydrogen permeance of >2 SCFH/ft{sup 2}.psi was obtained which was stable during the entire test, meeting the permeance associated with the 2010 DOE target flux. Lastly, the Mo{sub 2}C/V composite membranes were shown to be stable for at least 168 hours = one week, including cycling at high temperature and alternating He/H{sub 2} exposure.

  17. Detection of hydrogen attack in base metal and weld HAZ

    SciTech Connect

    Birring, A.S.; Elliot, J.; Hsiao, C.P.

    1995-12-01

    Hydrogen attack is known to occur in C-1/2Mo steels operating at high temperature and pressure in the hydrogen environment. The attack occurs in the base metal as well as in the weld heat affected zone (HAZ) of vessels and pipes. Hydrogen attack reduces the strength and toughness of steel and, if left undetected, can lead to component failure. Failures can be avoided by timely application of reliable and sensitive nondestructive techniques. Ultrasonic techniques were developed and applied to detect hydrogen attack in both the base metal and weld HAZ attack. Ultrasonic backscatter and velocity ratio techniques were applied for detection of base metal attack. These techniques are, however, not suitable for detection of HAZ attack. Conventional shear wave examination is currently used for HAZ inspection. This method can detect large cracks but is not sensitive to detect microcracks produced by hydrogen attack. A combination of two techniques was developed for detection of HAZ attack. These techniques are: contact focused angle beam S-wave and pitch-catch L-wave. The first technique focuses the beam using an acoustic lens while the second technique uses the intersection point of the two pitch-catch beam axes to illuminate the HAZ zone. Both the focused and pitch-catch techniques were applied on samples with simulated HAZ attack. The techniques were successful in detecting simulated attack.

  18. Using Hydrogen Balloons to Display Metal Ion Spectra

    ERIC Educational Resources Information Center

    Maynard, James H.

    2008-01-01

    We have optimized a procedure for igniting hydrogen-filled balloons containing metal salts to obtain the brightest possible flash while minimizing the quantity of airborne combustion products. We report air quality measurements in a lecture hall immediately after the demonstration. While we recommend that this demonstration be done outdoors or in

  19. Using Hydrogen Balloons to Display Metal Ion Spectra

    ERIC Educational Resources Information Center

    Maynard, James H.

    2008-01-01

    We have optimized a procedure for igniting hydrogen-filled balloons containing metal salts to obtain the brightest possible flash while minimizing the quantity of airborne combustion products. We report air quality measurements in a lecture hall immediately after the demonstration. While we recommend that this demonstration be done outdoors or in…

  20. Hydrogen-Rich Medium Attenuated Lipopolysaccharide-Induced Monocyte-Endothelial Cell Adhesion and Vascular Endothelial Permeability via Rho-Associated Coiled-Coil Protein Kinase.

    PubMed

    Xie, Keliang; Wang, Weina; Chen, Hongguang; Han, Huanzhi; Liu, Daquan; Wang, Guolin; Yu, Yonghao

    2015-07-01

    Sepsis is the leading cause of death in critically ill patients. In recent years, molecular hydrogen, as an effective free radical scavenger, has been shown a selective antioxidant and anti-inflammatory effect, and it is beneficial in the treatment of sepsis. Rho-associated coiled-coil protein kinase (ROCK) participates in junction between normal cells, and regulates vascular endothelial permeability. In this study, we used lipopolysaccharide to stimulate vascular endothelial cells and explored the effects of hydrogen-rich medium on the regulation of adhesion of monocytes to endothelial cells and vascular endothelial permeability. We found that hydrogen-rich medium could inhibit adhesion of monocytes to endothelial cells and decrease levels of adhesion molecules, whereas the levels of transepithelial/endothelial electrical resistance values and the expression of vascular endothelial cadherin were increased after hydrogen-rich medium treatment. Moreover, hydrogen-rich medium could lessen the expression of ROCK, as a similar effect of its inhibitor Y-27632. In addition, hydrogen-rich medium could also inhibit adhesion of polymorphonuclear neutrophils to endothelial cells. In conclusion, hydrogen-rich medium could regulate adhesion of monocytes/polymorphonuclear neutrophils to endothelial cells and vascular endothelial permeability, and this effect might be related to the decreased expression of ROCK protein. PMID:25895142

  1. Ultra-low percolation threshold in ferrite-metal cofired ceramics brings both high permeability and high permittivity

    NASA Astrophysics Data System (ADS)

    Wang, Liang; Bai, Yang; Lu, Xuefei; Cao, Jiang-Li; Qiao, Li-Jie

    2015-01-01

    High permeability and high permittivity are hard to be achieved simultaneously, either in single-phased materials or in composite materials, such as ferrite-ferroelectric ceramic composites and ferrite-metal percolative composites. In this work, ultra-low percolation threshold is achieved in NiZnCu ferrite-Ag cofired ceramics, which endows the composite with both high permeability and high permittivity by minimizing the negative effect of nonmagnetic conductive fillers on magnetic properties. The percolation threshold is controlled by the temperature matching between ferrite densification and Ag melting. A thin and long percolative net forms between large ferrite grains under a proper cofiring process, which brings a low percolation threshold of 1.21vol%, more than one order of magnitude lower than the theoretical value of 16vol%. Near the ultra-low threshold, the composite exhibits a high permeability of 585 and a high permittivity of 78.

  2. Ultra-low percolation threshold in ferrite-metal cofired ceramics brings both high permeability and high permittivity

    PubMed Central

    Wang, Liang; Bai, Yang; Lu, Xuefei; Cao, Jiang-Li; Qiao, Li-Jie

    2015-01-01

    High permeability and high permittivity are hard to be achieved simultaneously, either in single-phased materials or in composite materials, such as ferrite-ferroelectric ceramic composites and ferrite-metal percolative composites. In this work, ultra-low percolation threshold is achieved in NiZnCu ferrite-Ag cofired ceramics, which endows the composite with both high permeability and high permittivity by minimizing the negative effect of nonmagnetic conductive fillers on magnetic properties. The percolation threshold is controlled by the temperature matching between ferrite densification and Ag melting. A thin and long percolative net forms between large ferrite grains under a proper cofiring process, which brings a low percolation threshold of 1.21vol%, more than one order of magnitude lower than the theoretical value of 16vol%. Near the ultra-low threshold, the composite exhibits a high permeability of 585 and a high permittivity of 78. PMID:25557935

  3. A crossover from metal to plasma in dense fluid hydrogen

    NASA Astrophysics Data System (ADS)

    Sumi, Tomonari; Sekino, Hideo

    2006-11-01

    Thermodynamic properties in dense fluid hydrogen are studied by using a density-functional theory for electron-proton binary mixtures that is called quantal hypernetted-chain (QHNC) integral equation. A nonlocal approximation for the exchange-correlation potential in a finite-temperature Kohn-Sham equation is presented. Results obtained from the QHNC with the nonlocal approximation are compared with those obtained from the QHNC with a local density approximation. Temperature variation of thermodynamic quantities between 104 and 106K are investigated along an isochor specified by a dimensionless density parameter of rs=0.5. These quantities obtained from the QHNCs show that a crossover from metal to plasma occurs around a temperature of T =1.78105K. Electrical resistivity Re of the dense fluid hydrogen evaluated from a Ziman formula [The Properties of Liquid Metals, edited by S. Takenohi (Wiley, New York, 1973)] extended to finite temperature is about 0.7??cm at T =104K. The dense fluid hydrogen at the temperature can be considered as a metallic fluid, because the value is smaller than typical values of Re in alkali metals at room temperature. The Re slightly increases with the temperature increase, and the temperature valuation of Re is monotonic. We clearly show that the contribution from the electronic excited states plays an important role for the sharp crossover from the metal to the plasma, and that the crossover is interpreted as a crossover from degenerate electron gas to nondegenerate electron gas.

  4. The metallization and superconductivity of dense hydrogen sulfide

    SciTech Connect

    Li, Yinwei Hao, Jian; Li, Yanling; Liu, Hanyu; Ma, Yanming

    2014-05-07

    Hydrogen sulfide (H{sub 2}S) is a prototype molecular system and a sister molecule of water (H{sub 2}O). The phase diagram of solid H{sub 2}S at high pressures remains largely unexplored arising from the challenges in dealing with the pressure-induced weakening of S–H bond and larger atomic core difference between H and S. Metallization is yet achieved for H{sub 2}O, but it was observed for H{sub 2}S above 96 GPa. However, the metallic structure of H{sub 2}S remains elusive, greatly impeding the understanding of its metallicity and the potential superconductivity. We have performed an extensive structural study on solid H{sub 2}S at pressure ranges of 10–200 GPa through an unbiased structure prediction method based on particle swarm optimization algorithm. Besides the findings of candidate structures for nonmetallic phases IV and V, we are able to establish stable metallic structures violating an earlier proposal of elemental decomposition into sulfur and hydrogen [R. Rousseau, M. Boero, M. Bernasconi, M. Parrinello, and K. Terakura, Phys. Rev. Lett. 85, 1254 (2000)]. Our study unravels a superconductive potential of metallic H{sub 2}S with an estimated maximal transition temperature of ∼80 K at 160 GPa, higher than those predicted for most archetypal hydrogen-containing compounds (e.g., SiH{sub 4}, GeH{sub 4}, etc.)

  5. High pressure/high temperature hydrogen permeability in candidate Stirling engine alloys

    SciTech Connect

    Bhattacharyya, S.; Vesely, E.J. Jr.; Hill, V.L.

    1982-03-01

    Hydrogen permeation tests of eight high-temperature alloys were conducted in 20.7 MPa hydrogen at 923 to 1088 K for assessing suitability in Stirling engine application for heater head and heater head tubing. The iron-nickel-base alloys investigated included N-155, Incoloy 800 (IN 800), A-286, and 19-9DL, and cast alloys CRM-6D, SAF-11, and XF-818. Low carbon alloys Stellite 6B (6BLC), a cobalt-base wrought alloy, was also investigated. 15 refs.

  6. Metal hydride hydrogen compression: Recent advances and future prospects

    DOE PAGESBeta

    Bowman, Jr., Robert C.; Yartys, Volodymyr A.; Lototskyy, Mykhaylo V.; Linkov, Vladimir; Grant, David; Stuart, Alastair; Eriksen, Jon; Denys, Roman

    2016-03-17

    Metal hydride (MH) thermal sorption compression is one of the more important applications of the metal hydrides. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units are analyzed. The paper includes also a theoretical modeling of a two-stage compressor aimed at both describing the performance of the experimentally studied systems, but, also, on their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS andmore » the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the metal hydride compression in the overall development of the hydrogen driven energy systems. Lastly, the work is based on the analysis of the development of the technology in Europe, USA and South Africa.« less

  7. On-board hydrogen storage system using metal hydride

    SciTech Connect

    Heung, L.K.

    1997-07-01

    A hydrogen powered hybrid electric bus has been developed for demonstration in normal city bus service in the City of Augusta, Georgia, USA. The development team, called H2Fuel Bus Team, consists of representatives from government, industry and research institutions. The bus uses hydrogen to fuel an internal combustion engine which drives an electric generator. The generator charges a set of batteries which runs the electric bus. The hydrogen fuel and the hybrid concept combine to achieve the goal of near-zero emission and high fuel efficiency. The hydrogen fuel is stored in a solid form using an on-board metal hydride storage system. The system was designed for a hydrogen capacity of 25 kg. It uses the engine coolant for heat to generate a discharge pressure higher than 6 atm. The operation conditions are temperature from ambient to 70 degrees C, hydrogen discharge rate to 6 kg/hr, and refueling time 1.5 hours. Preliminary tests showed that the performance of the on-board storage system exceeded the design requirements. Long term tests have been planned to begin in 2 months. This paper discusses the design and performance of the on-board hydrogen storage system.

  8. Replacing precious metals with carbide catalysts for hydrogenation reactions

    SciTech Connect

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo?C and Ni/Mo?C) catalysts were compared with Pd/SiO? for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO?, Mo?C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo?C could be completely regenerated by H? treatment at 723 K for the three molecules. The Ni modified Mo?C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Ni modified Mo?C catalysts, 8.6%Ni/Mo?C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO?. Compared to Pd/SiO?, both Mo?C and Ni/Mo?C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.

  9. Replacing precious metals with carbide catalysts for hydrogenation reactions

    DOE PAGESBeta

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Nimore » modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.« less

  10. Replacing precious metals with carbide catalysts for hydrogenation reactions

    SciTech Connect

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Ni modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.

  11. Noble-metal-free plasmonic photocatalyst: hydrogen doped semiconductors

    PubMed Central

    Ma, Xiangchao; Dai, Ying; Yu, Lin; Huang, Baibiao

    2014-01-01

    The unique capacity of localized surface plasmon resonance (LSPR) offers a new opportunity to overcome the limited efficiency of semiconductor photocatalyst. Here we unravel that LSPR, which usually occurs in noble metal nanoparticles, can be realized by hydrogen doping in noble-metal-free semiconductor using TiO2 as a model photocatalyst. Moreover, its LSPR is located in infrared region, which supplements that of noble metal whose LSPR is generally in the visible region, making it possible to extend the light response of photocatalyst to infrared region. The near field enhancement is shown to be comparable with that of noble-metal nanoparticles, indicating that highly enhanced light absorption rate can be expected. The present work can provide a key guideline for the creation of highly efficient noble-metal-free plasmonic photocatalysts and have a much wider impact in infrared bioimaging and spectroscopy where infrared LSPR is essential. PMID:24496400

  12. Interplay between metal???? interactions and hydrogen bonds: some unusual synergetic effects of coinage metals and substituents.

    PubMed

    Gao, Meng; Yang, Xin; Cheng, Jianbo; Li, Qingzhong; Li, Wenzuo; Loffredo, Robert E

    2013-10-01

    The ternary systems of C(2)H(4) (C(2)H(2) or C(6)H(6))-MCN-HF (M=Cu, Ag, Au) and the respective binary systems were investigated to study the interplay between metal???? interactions and hydrogen bonds. The metal???? interactions in C(2)H(4)-MCN become stronger with the irregular order Aghydrogen bonds in MCN-HF become weaker following the same order. The metal???? interactions are weakened as the H atoms in the ? system are replaced with electron-withdrawing groups and enhanced by electron-donating groups. Type 1 of these ternary systems, in which MCN acts as Lewis base and acid simultaneously, is more stable than type 2, in which C(2)H(4) acts as a double Lewis base. Negative cooperativity is present in type 2 ternary systems with a weakening of the metal???? interactions and the hydrogen bonds. Positive cooperativity is found in type 1 ternary systems with an enhancement of the metal???? interactions and the hydrogen bonds, except for C(2)(CN)(4)-AuCN-HF-1. The weaker metal???? interaction in C(6)H(6)-AuCN has a greater enhancing effect on the hydrogen bond in AuCN-HF than those in C(2)H(4)-AuCN and C(2)H(2)-AuCN. These synergetic effects were analyzed with the natural bond orbital and energy decomposition. PMID:23893522

  13. Nanoparticulate gellants for metallized gelled liquid hydrogen with aluminum

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan; Starkovich, John; Adams, Scott

    1996-01-01

    Gelled liquid hydrogen was experimentally formulated using sol-gel technology. As a follow-on to work with cryogenic simulants, hydrogen was gelled with an alkoxide material: BTMSE. Initial results demonstrated that gellants with a specific surface area of 1000 m(exp 2)/g could be repeatably fabricated. Gelled hexane and metallized gelled hexane (with 13.8-wt% Al) were produced. Propellant settling testing was conducted for acceleration levels of 2 to 10 times normal gravity and a minimum gellant percentage was determined for stable gelled hexane and metalized gelled hexane. A cryogenic capillary rheometer was also designed, constructed, and used to determine the viscosity of gelled hydrogen. Small volumes of liquid hydrogen were gelled with a 7- to 8-wt% gellant level. The gelled H2 viscosity was 1.5 to 3.7 times that of liquid hydrogen: 0.048 to 0.116 mPa-s versus 0.03 mPa-s for liquid H2 (at 16 K and approximately 1 atm pressure).

  14. Composite hydrogen separation element and module

    DOEpatents

    Edlund, D.J.

    1996-03-12

    There are disclosed improvements in multicomponent composite metal membranes useful for the separation of hydrogen, the improvements comprising the provision of a flexible porous intermediate layer between a support layer and a nonporous hydrogen-permeable coating metal layer, and the provision of a textured coating metal layer. 15 figs.

  15. Organic substrates as electron donors in permeable reactive barriers for removal of heavy metals from acid mine drainage.

    PubMed

    Kijjanapanich, P; Pakdeerattanamint, K; Lens, P N L; Annachhatre, A P

    2012-12-01

    This research was conducted to select suitable natural organic substrates as potential carbon sources for use as electron donors for biological sulphate reduction in a permeable reactive barrier (PRB). A number of organic substrates were assessed through batch and continuous column experiments under anaerobic conditions with acid mine drainage (AMD) obtained from an abandoned lignite coal mine. To keep the heavy metal concentration at a constant level, the AMD was supplemented with heavy metals whenever necessary. Under anaerobic conditions, sulphate-reducing bacteria (SRB) converted sulphate into sulphide using the organic substrates as electron donors. The sulphide that was generated precipitated heavy metals as metal sulphides. Organic substrates, which yielded the highest sulphate reduction in batch tests, were selected for continuous column experiments which lasted over 200 days. A mixture of pig-farm wastewater treatment sludge, rice husk and coconut husk chips yielded the best heavy metal (Fe, Cu, Zn and Mn) removal efficiencies of over 90%. PMID:23437664

  16. Hydrogen and Materials: Influence of the Hydrogen Environment on the Metallic Materials Behavior

    SciTech Connect

    Lamani, Emil; Jouinot, Patrice

    2010-01-21

    The materials sensitivity to hydrogen is studied and measured in this work using the disk pressure testing, whose principle is the comparison of the rupture parameters obtained with metallic membranes tested similarly under helium and hydrogen. Such technique allows various studies and reveals parameters that remain not significant with less sensitive methods. This work presents an overview of numerous experimental results concerning the influence of various factors (material and gas composition, mechanical and heat treatments, type of microstructure...) on the hydrogen embrittlement of ferrous and nonferrous alloys. There are shown synergies between such factors, related to physical and metallurgical phenomena and we give some practical considerations, which can be useful for the evaluation of the safety offered by different materials in contact with hydrogen and for searching ways to improve their behavior.

  17. Hydrogen evolution from water through metal sulfide reactions

    SciTech Connect

    Saha, Arjun; Raghavachari, Krishnan

    2013-11-28

    Transition metal sulfides play an important catalytic role in many chemical reactions. In this work, we have conducted a careful computational study of the structures, electronic states, and reactivity of metal sulfide cluster anions M{sub 2}S{sub X}{sup −} (M = Mo and W, X = 4–6) using density functional theory. Detailed structural analysis shows that these metal sulfide anions have ground state isomers with two bridging sulfide bonds, notably different in some cases from the corresponding oxides with the same stoichiometry. The chemical reactivity of these metal sulfide anions with water has also been carried out. After a thorough search on the reactive potential energy surface, we propose several competitive, energetically favorable, reaction pathways that lead to the evolution of hydrogen. Selectivity in the initial water addition and subsequent hydrogen migration are found to be the key steps in all the proposed reaction channels. Initial adsorption of water is most favored involving a terminal metal sulfur bond in Mo{sub 2}S{sub 4}{sup −} isomers whereas the most preferred orientation for water addition involves a bridging metal sulfur bond in the case of W{sub 2}S{sub 4}{sup −} and M{sub 2}S{sub 5}{sup −} isomers. In all the lowest energy H{sub 2} elimination steps, the interacting hydrogen atoms involve a metal hydride and a metal hydroxide (or thiol) group. We have also observed a higher energy reaction channel where the interacting hydrogen atoms in the H{sub 2} elimination step involve a thiol (–SH) and a hydroxyl (–OH) group. For all the reaction pathways, the Mo sulfide reactions involve a higher barrier than the corresponding W analogues. We observe for both metals that reactions of M{sub 2}S{sub 4}{sup −} and M{sub 2}S{sub 5}{sup −} clusters with water to liberate H{sub 2} are exothermic and involve modest free energy barriers. However, the reaction of water with M{sub 2}S{sub 6}{sup −} is highly endothermic with a considerable barrier due to saturation of the local bonding environment.

  18. Hot Hydrogen Testing of Refractory Metals and Ceramics

    NASA Technical Reports Server (NTRS)

    Zee, Ralph; Chin, Bryan; Cohron, Jon

    1993-01-01

    The objective of this investigation is to develop a technique with which refractory metal carbide samples can be exposed to hydrogen containing gases at high temperatures, and to use various microstructural and analytical techniques to determine the chemical and rate processes involved in hydrogen degradation in these materials. Five types of carbides were examined including WC, NbC, HfC, ZrC, and TaC. The ceramics were purchased and were all monolithic in nature. The temperature range investigated was from 850 to 1600 C with a hydrogen pressure of one atmosphere. Control experiments, in vacuum, were also conducted for comparison so that the net effects due to hydrogen could be isolated. The samples were analyzed prior to and after exposure. Gas samples were collected in selected experiments and analyzed using gas chromography. Characterization of the resulting microstructure after exposure to hydrogen was conducted using optical microscopy, x-ray diffraction, scanning electron microscopy, and weight change. The ceramics were purchased and were all monolithic in nature. It was found that all samples lost weight after exposure, both in hydrogen and vacuum. Results from the microstructure analyses show that the degradation processes are different among the five types of ceramics involved. In addition, the apparent activation energy for the degradation process is a function of temperature even within the same material. This indicates that there are more than one mechanism involved in each material, and that the mechanisms are temperature dependent.

  19. Graphene physics and insulator-metal transition in compressed hydrogen

    NASA Astrophysics Data System (ADS)

    Naumov, Ivan I.; Cohen, R. E.; Hemley, Russell J.

    2014-03-01

    As established recently both theoretically and experimentally, compressed hydrogen passes through a series of layered structures in which the layers can be viewed as distorted graphene sheets. These structures and their electronic properties can be understood by studying simple model systems-(i) a H6 ring, (ii) an ideal single hydrogen graphene sheet and (iii) three-dimensional model lattices consisting of such sheets. The energetically stable structures result from structural distortions of model graphene-based systems due to electronic instabilities towards Peierls or other distortions associated with the opening of a bandgap. Two factors play crucial roles in the metallization of compressed hydrogen: (i) crossing of conduction and valence bands in hexagonal or grapheme-like layers due to topology and (ii) formation of bonding states with 2pz π character. This research was supported by EFree, an Energy Frontier Research Centerfunded by the US Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0001057.

  20. Metallization and electrical conductivity of hydrogen in Jupiter.

    PubMed

    Nellis, W J; Weir, S T; Mitchell, A C

    1996-08-16

    Electrical conductivities of molecular hydrogen in Jupiter were calculated by scaling electrical conductivities measured at shock pressures in the range of 10 to 180 gigapascals (0.1 to 1.8 megabars) and temperatures to 4000 kelvin, representative of conditions inside Jupiter. Jupiter's magnetic field is caused by convective dynamo motion of electrically conducting fluid hydrogen. The data imply that Jupiter should become metallic at 140 gigapascals in the fluid, and the electrical conductivity in the jovian molecular envelope at pressures up to metallization is about an order of magnitude larger than expected previously. The large magnetic field is produced in the molecular envelope closer to the surface than previously thought. PMID:8688072

  1. Prospects for obtaining metallic hydrogen with spherical presses

    NASA Technical Reports Server (NTRS)

    Spain, I. L.; Ishizaki, K.; Marchello, J. M.; Paauwe, J.

    1973-01-01

    Description of a split-sphere apparatus modified for use at low temperature and affording a possible method for compressing molecular hydrogen to a pressure in excess of 1 Mbar and for converting it to the metallic state. The construction costs of the apparatus are relatively low and the amount of liquid helium required for low-temperature operation is readily obtainable with modern liquefiers.

  2. Molecular Hydrogen Interactions Within Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Fitzgerald, S.; Pierce, C.; Schloss, J.; Thompson, B.; Rowsell, J.

    2011-06-01

    There is much interest in understanding the details of molecular hydrogen physisorption within highly porous materials that could be used for hydrogen storage applications. Unfortunately, the structures of the most promising materials are too complex for ab inito calculations and DFT models are notoriously unreliable for weak interactions. A new approach based on so-called van der Waals DFT has been proposed for explaining the behavior of molecular hydrogen within metal-organic frameworks.1 In this talk we will present IR spectra of adsorbed hydrogen within a series of isostructural MOFs containing Mg2+ and various first-row transition metal cations. The data clearly show that H2 binds first at an open metal site, with a large vibrational redshift that correlates with the magnitude of the site binding energy. These spectra show minimal effects due to H2\\cdot\\cdotCdotH2 interactions and are significantly different from the recent findings of the Chabal group.1 After collecting spectra over a wide range of temperature and H2 pressure, we could only reproduce their experimental observations by exposing samples to moist air, which is well-known to cause occupation of the open metal sites by water. This calls into question the appropriateness of the van der Waals DFT models that were used to support their interpretations.1 We are hopeful that the spectra we present will inspire improved parametrization of such advanced computational models, or prompt the development of superior ones. 1. Nijjem et al., J. Am. Chem. Soc. 132, 14834 (2010).

  3. Zero-Temperature Structures of Atomic Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    McMahon, Jeffrey; Ceperley, David

    2011-03-01

    Since the first prediction of an atomic metallic phase of hydrogen by Wigner and Huntington over 75 years ago, there have been many theoretical efforts aimed at determining the crystal structures of the zero-temperature phases. We present results from ab initio random structure searching with density functional theory performed to determine the ground state structures from 500 GPa to 5 TPa. We estimate that molecular hydrogen dissociates into a monatomic body-centered tetragonal structure near 500 GPa (rs = 1.225), which then remains stable to 2.5 TPa (rs = 0.969). At higher pressures, hydrogen stabilizes in an . . . ABCABC . . . planar structure that is remarkably similar to the ground state of lithium, which compresses to the face-centered cubic lattice beyond 5 TPa (rs < 0.86). Our results provide a complete ab initio description of the atomic metallic crystal structures of hydrogen, resolving one of the most fundamental and long outstanding issues concerning the structures of the elements.

  4. A van der Waals density functional theory comparison of metal decorated graphene systems for hydrogen adsorption

    NASA Astrophysics Data System (ADS)

    Wong, Janet; Yadav, Shwetank; Tam, Jasmine; Veer Singh, Chandra

    2014-06-01

    Previous Density Functional Theory (DFT) studies on metal decorated graphene generally use local density approximation (LDA) or generalized gradient approximation (GGA) functionals which can cause inaccuracies in hydrogen binding energies as they neglect van der Waals (vdW) interactions and are difficult to compare due to their widely varying simulation parameters. We investigated the hydrogen binding ability of several metals with a consistent set of simulations using the GGA functional and incorporated vdW forces through the vdW-DF2 functional. Metal adatom anchoring on graphene and hydrogen adsorption ability for both single and double sided decoration were studied for eight metals (Al, Li, Na, Ca, Cu, Ni, Pd, and Pt). It was found that the vdW correction can have a significant impact on both metal and hydrogen binding energies. The vdW-DF2 functional led to stronger metal adatom and hydrogen binding for light metals in comparison to GGA results, while heavier transition metals displayed the opposite behaviour but still produced stronger hydrogen binding energies than light metals. Nickel was found to be the best balance between hydrogen binding ability for reversible storage and low weight. The effects on hydrogen binding energy and maximum achievable hydrogen gravimetric density were analyzed for Ni-graphene systems with varying metal coverage. Lower metal coverage was found to improve hydrogen binding but decrease hydrogen gravimetric density. The highest achieved Ni-graphene system gravimetric density was 6.12 wt. %.

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

    PubMed

    Sunger, Neha; Bose, Purnendu

    2009-09-01

    Hydrogenotrophic denitrification was demonstrated using hydrogen generated from anoxic corrosion of metallic iron. For this purpose, a mixture of hydrogenated water and nitrate solution was used as reactor feed. A semi-batch reactor with nitrate loading of 2000 mg m(-3) d(-1) and hydraulic retention time (HRT) of 50 days produced effluent with nitrate concentration of 0.27 mg N L(-1) (99% nitrate removal). A continuous flow reactor with nitrate loading of 28.9 mg m(-3) d(-1) and HRT of 15.6 days produced effluent with nitrate concentration of approximately 0.025 mg N L(-1) (95% nitrate removal). In both cases, the concentration of nitrate degradation by-products, viz., ammonia and nitrite, were below detection limits. The rate of denitrification in the reactors was controlled by hydrogen availability, and hence to operate such reactors at higher nitrate loading rates and/or lower HRT than reported in the present study, hydrogen concentration in the hydrogenated water must be significantly increased. PMID:19398198

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

    PubMed

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

    2011-04-01

    Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg(-1); ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria--absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH(2) has a ?Hf~75 kJ mol(-1)), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts. PMID:21399630

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

    NASA Technical Reports Server (NTRS)

    Easter, R. W.

    1974-01-01

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

  8. The solubility of hydrogen and deuterium in alloyed, unalloyed and impure plutonium metal

    SciTech Connect

    Richmond, Scott; Bridgewater, Jon S; Ward, John W; Allen, Thomas H

    2010-01-01

    Hydrogen is exothermically absorbed in many transition metals, all rare earths and the actinides. The hydrogen gas adsorbs, dissociates and diffuses into these metals as atomic hydrogen. Absorbed hydrogen is generally detrimental to Pu, altering its properties and greatly enhancing corrosion. Measuring the heat of solution of hydrogen in Pu and its alloys provides significant insight into the thermodynamics driving these changes. Hydrogen is present in all Pu metal unless great care is taken to avoid it. Heats of solution and formation are provided along with evidence for spinodal decomposition.

  9. Structure, mechanical properties, and hydrogen permeability of Pd-Cu and Pd-Ru membrane foils prepared by magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Ievlev, V. M.; Burkhanov, G. S.; Roshan, N. R.; Belonogov, E. K.; Maksimenko, A. A.; Dontsov, A. I.; Rudakov, K. E.

    2012-11-01

    Magnetron sputtering is used to prepare thin (down to 7 ?m) Pd-Cu and Pd-Ru membrane foils deposited on the surface of a SiO2/Si heterostructure at 300 and 700 K. Condensed foils (CFs) of an ordered Pd-Cu solid solution (? phase with a CsCl-type structure) and a Pd-Ru solid solution (fcc lattice) are synthesized for the first time. The foils of both alloys are characterized by a gradient granular structure due to selective development of <110> and <112> textures and a <111> texture in the Pd-Cu and Pd-Ru foils during their deposition, respectively. The hardness of the free surface of both foils removed from the substrate is determined by nanoindentation. The hardness is 3.0-3.6 GPa and is 20-50% lower than that of the contact surface (at the interface with the substrate) owing to the gradient structure. The hydrogen permeability of the Pd-Cu CF (? phase) is higher than that of the Pd CF by almost an order of magnitude (effect of a less dense crystal lattice) and is 5-7 times higher than those of the Pd-Ru CF and the Pd-Cu foil prepared by rolling.

  10. Hydrogen-induced reconstruction of transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Mller, Klaus

    1993-04-01

    This study compares the results of a number of recent papers on hydrogen adsorption on Rh(110), Rh(311) and Fe(211) as well as on Ni(111) and Fe(110) surfaces. It particularly deals with the structural aspect of these low energy electron diffraction (LEED) investigations and correlates them, if available, with respective thermodesorption data. Upon dissociative adsorption by a non activated process hydrogen induces local displacements of the atoms about the adsorption sites. With increasing coverage these displacements order to form a sequence of weakly reconstructed phases and gradually lift the surface layer relaxation of the formerly clean surface. Along close packed rows of metal surface atoms hydrogen atoms tend to occupy threefold coordinated adsorption sites which, in turn, arrange in single or double chains. The coverage dependent periodicity of these adlayer structure elements together with the respective shift buckling of the substrate surface generates the observed superstructures. Since not only open but also close packed surfaces show this weak (and sometimes strong) reconstruction upon hydrogen adsorption it should be generally considered in all adsorption systems.

  11. Transport properties of liquid metal hydrogen under high pressures

    NASA Technical Reports Server (NTRS)

    Brown, R. C.; March, N. H.

    1972-01-01

    A theory is developed for the compressibility and transport properties of liquid metallic hydrogen, near to its melting point and under high pressure. The interionic force law is assumed to be of the screened Coulomb type, because hydrogen has no core electrons. The random phase approximation is used to obtain the structure factor S(k) of the system in terms of the Fourier transform of this force law. The long wavelenth limit of the structure factor S(o) is related to the compressibility, which is much lower than that of alkali metals at their melting points. The diffusion constant at the melting point is obtained in terms of the Debye frequency, using a frequency spectrum analogous with the phonon spectrum of a solid. A similar argument is used to obtain the combined shear and bulk viscosities, but these depend also on S(o). The transport coefficients are found to be about the same size as those of alkali metals at their melting points.

  12. Thermal method for fabricating a hydrogen separation membrane on a porous substrate

    DOEpatents

    Song, Sun-Ju (Orland Park, IL); Lee, Tae H. (Naperville, IL); Chen, Ling (Woodridge, IL); Dorris, Stephen E. (LaGrange Park, IL); Balachandran, Uthamalingam (Hinsdale, IL)

    2009-10-20

    A thermal method of making a hydrogen permeable composition is disclosed. A mixture of metal oxide powder and ceramic oxide powder and optionally a pore former is formed and pressed to form an article. The article is dried at elevated temperatures and then sintered in a reducing atmosphere to provide a dense hydrogen permeable portion near the surface of the sintered mixture. The dense hydrogen permeable portion has a higher initial concentration of metal than the remainder of the sintered mixture and is present in the range of from about 20 to about 80 percent by volume of the dense hydrogen permeable portion.

  13. Advanced Hydrogen Transport Membranes for Vision 21 Fossil Fuel Plants

    SciTech Connect

    Carl R. Evenson; Harold A. Wright; Adam E. Calihman; U. Balachandran; Richard N. Kleiner; James E. Stephan; Frank E. Anderson; Chandra Ratnasamy; Mahendra Sunkara; Jyothish Thangala; Clive Brereton; Warren Wolfs; James Lockhart

    2005-10-31

    During this quarter composite layered membrane size was scaled-up and tested for permeation performance. Sintering conditions were optimized for a new cermet containing a high permeability metal and seals were developed to allow permeability testing. Theoretical calculations were performed to determine potential sulfur tolerant hydrogen dissociation catalysts. Finally, work was finalized on mechanical and process & control documentation for a hydrogen separation unit.

  14. Phase separation of metallic hydrogen-helium alloys

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1976-01-01

    Calculations are presented for the thermodynamic functions and phase separation boundaries of solid metallic hydrogen helium alloys at temperatures between 0 K and 19,000 K and at pressures between 15 and 90 megabars. Expressions for the band structure energy of a randomly disordered alloy (including third order in the electron ion interaction) are derived and evaluated. Short and long range order are included by the quasi-chemical method, and lattice dynamics in the virtual crystal harmonic approximation. We conclude that at temperatures below 4,000 K there is complete phase separation of hydrogen helium alloys, and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  15. Phase separation of metallic hydrogen-helium alloys

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1977-01-01

    Calculations are presented for the thermodynamic functions and phase-separation boundaries of solid metallic hydrogen-helium alloys at temperatures between zero and 19,000 K and at pressures between 15 and 90 Mbar. Expressions for the band-structure energy of a randomly disordered alloy (including third order in the electron-ion interaction) are derived and evaluated. Short- and long-range orders are included by the quasi-chemical method, and lattice dynamics in the virtual-crystal harmonic approximation. It is concluded that at temperatures below 4000 K, there is essentially complete phase separation of hydrogen-helium alloys and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  16. Capture of liquid hydrogen boiloff with metal hydride absorbers

    NASA Technical Reports Server (NTRS)

    Rosso, M. J.; Golben, P. M.

    1984-01-01

    A procedure which uses metal hydrides to capture some of this low pressure (,1 psig) hydrogen for subsequent reliquefaction is described. Of the five normally occurring sources of boil-off vapor the stream associated with the off-loading of liquid tankers during dewar refill was identified as the most cost effective and readily recoverable. The design, fabrication and testing of a proof-of-concept capture device, operating at a rate that is commensurate with the evolution of vapor by the target stream, is described. Liberation of the captured hydrogen gas at pressure .15 psig at normal temperatures (typical liquefier compressor suction pressure) are also demonstrated. A payback time of less than three years is projected.

  17. The transition to the metallic state in low density hydrogen

    NASA Astrophysics Data System (ADS)

    McMinis, Jeremy; Morales, Miguel A.; Ceperley, David M.; Kim, Jeongnim

    2015-11-01

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of rs = 2.27(3) a0. We compare our results to previously reported density functional theory, Hedin's GW approximation, and dynamical mean field theory results.

  18. The transition to the metallic state in low density hydrogen.

    PubMed

    McMinis, Jeremy; Morales, Miguel A; Ceperley, David M; Kim, Jeongnim

    2015-11-21

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of rs = 2.27(3) a0. We compare our results to previously reported density functional theory, Hedin's GW approximation, and dynamical mean field theory results. PMID:26590549

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

    DOEpatents

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

    2008-06-10

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

  20. Stainless Steel Permeability

    SciTech Connect

    Buchenauer, Dean A.; Karnesky, Richard A.

    2015-09-01

    An understanding of the behavior of hydrogen isotopes in materials is critical to predicting tritium transport in structural metals (at high pressure), estimating tritium losses during production (fission environment), and predicting in-vessel inventory for future fusion devices (plasma driven permeation). Current models often assume equilibrium diffusivity and solubility for a class of materials (e.g. stainless steels or aluminum alloys), neglecting trapping effects or, at best, considering a single population of trapping sites. Permeation and trapping studies of the particular castings and forgings enable greater confidence and reduced margins in the models. For FY15, we have continued our investigation of the role of ferrite in permeation for steels of interest to GTS, through measurements of the duplex steel 2507. We also initiated an investigation of the permeability in work hardened materials, to follow up on earlier observations of unusual permeability in a particular region of 304L forgings. Samples were prepared and characterized for ferrite content and coated with palladium to prevent oxidation. Issues with the poor reproducibility of measurements at low permeability were overcome, although the techniques in use are tedious. Funding through TPBAR and GTS were secured for a research grade quadrupole mass spectrometer (QMS) and replacement turbo pumps, which should improve the fidelity and throughput of measurements in FY16.

  1. High strength cored wire weld metal hydrogen content, and weld metal cracking

    SciTech Connect

    Hannerz, N.E.; Xu, L.C.

    1993-12-31

    Cored wires for high strength steel were tested for weld metal cracking with the G-BOP (Gap Bead on Plate) test. In all, 29 wires were gathered to yield rather a broad mixture of types and strength levels. Ten rutile, twelve basic flux cored wires, and seven metal cored wires were tested. G-BOP testing was performed at ambient but also at higher temperatures so that the preheating temperature could be evaluated. Gas shielding was used, wire diameter being 1.2 and 1.6 mm. Strength class of the wires varied from AWS E70 up to AWS E110. Altogether some 180 welds were studied for weld cracking, cracked bead area ranging from 2 to 100%. The 10% cracking preheat temperature, i.e., the temperature that might be recommended for practical welding ranged from ambient up to 150 C, at an arc energy of 1 kJ/mm. Distinct correlations were found between hydrogen content, weld metal carbon equivalent, heat input and tendency for cracking. Thus, from a weld metal cracking point of view, preheat and interpass temperatures must be considered important when going to low E{sub w} steels, like spray cooled TMCP steels, QT steels and the like. Hydrogen content varied from 1.45 ml/100 g of as deposited weld metal up to 14.8 ml/100 g, rutile wires yielding the highest hydrogen content. Weld metals within the strength classes AWS E90 to AWS E110 generally have low hydrogen content and basic flux formulation.

  2. Distinct Metallization and Atomization Transitions in Dense Liquid Hydrogen

    NASA Astrophysics Data System (ADS)

    Mazzola, Guglielmo; Sorella, Sandro

    2015-03-01

    We perform molecular dynamics simulations driven by accurate quantum Monte Carlo forces on dense liquid hydrogen. There is a recent report of a complete atomization transition between a mixed molecular-atomic liquid and a completely dissociated fluid in an almost unaccessible pressure range [Nat. Commun. 5, 3487 (2014)]. Here, instead, we identify a different transition between the fully molecular liquid and the mixed-atomic fluid at 400 GPa , i.e., in a much more interesting pressure range. We provide numerical evidence supporting the metallic behavior of this intermediate phase. Therefore, we predict that the metallization at finite temperature occurs in this partially dissociated molecular fluid, well before the complete atomization of the liquid. At high temperature this first-order transition becomes a crossover, in very good agreement with the experimental observation. Several systematic tests supporting the quality of our large scale calculations are also reported.

  3. Distinct metallization and atomization transitions in dense liquid hydrogen.

    PubMed

    Mazzola, Guglielmo; Sorella, Sandro

    2015-03-13

    We perform molecular dynamics simulations driven by accurate quantum Monte Carlo forces on dense liquid hydrogen. There is a recent report of a complete atomization transition between a mixed molecular-atomic liquid and a completely dissociated fluid in an almost unaccessible pressure range [Nat. Commun. 5, 3487 (2014)]. Here, instead, we identify a different transition between the fully molecular liquid and the mixed-atomic fluid at ?400??GPa, i.e., in a much more interesting pressure range. We provide numerical evidence supporting the metallic behavior of this intermediate phase. Therefore, we predict that the metallization at finite temperature occurs in this partially dissociated molecular fluid, well before the complete atomization of the liquid. At high temperature this first-order transition becomes a crossover, in very good agreement with the experimental observation. Several systematic tests supporting the quality of our large scale calculations are also reported. PMID:25815949

  4. Microscopic characterization of metal-carbon-hydrogen composites (metal = Li, Mg)

    NASA Astrophysics Data System (ADS)

    Isobe, Shigehito; Yamada, Sumito; Wang, Yongming; Hashimoto, Naoyuki; Ohnuki, Somei; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2013-09-01

    Li-C-H system, which can store about 5.0 mass% of rechargeable H2, has been reported as a promising hydrogen storage system by Ichikawa et al. [Appl. Phys. Lett. 86, 241914 (2005); Mater. Trans. 46, 1757 (2005)]. This system was investigated from the thermodynamic and structural viewpoints. However, hydrogen absorption/desorption mechanism and the state of hydrogen atoms absorbed in the composite have not been clarified yet. In order to find new or better hydrogen storage system, graphite powder and nano-structural graphite ball-milled under H2 and Ar atmosphere were prepared and milled with Li and Mg under Ar atmosphere in this study. Microstructural analysis for those samples by transmission electron microscope revealed that LiC6 and/or LiC12 were formed in Li-C-H system. On the other hand, MgC2 was found in Mg-C-H system ball-milled under H2 atmosphere, but not in the system ball-milled under Ar atmosphere. These results indicated that nano-structure in composites of nano-structural graphite is different from that of alkali (-earth) metal. For these reasons, metal-C-H system can be recognized to be a new family of hydrogen storage materials.

  5. Metal-Hydrogen Phase Diagrams in the Vicinity of Melting Temperatures

    SciTech Connect

    Shapovalov, V.I.

    1999-01-06

    Hydrogen-metal interaction phenomena belong to the most exciting challenges of today's physical metallurgy and physics of solids due to the uncommon behavior of hydrogen in condensed media and to the need for understanding hydrogen's strong negative impact on properties of some high-strength steels and.alloys. The paper cites and summarizes research data on fundamental thermodynamic characteristics of hydrogen in some metals that absorb it endothermally at elevated temperatures. For a number of metal-hydrogen systems, information on some phase diagrams previously not available to the English-speaking scientific community is presented.

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

    DOEpatents

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

    2015-02-24

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

  7. Preparation of thin metallic titanium foils as hydrogen targets.

    SciTech Connect

    Greene, J. P.; Lee, H. Y.; Becker, H.-W.; Physics; Ruhr Univ. Bochum

    2010-02-11

    In a recently proposed study to resolve the discrepancy for the cross-section from the inverse reaction {sup 21}Ne(p,{alpha}){sup 18}F, important in calculations of asymptotic giant branch (AGB) stellar nucleosynthesis, a hydrogen target was required. Another important consideration for studying this reaction involves the isotopic abundance of Ne measured in stellar silicon carbide (SiC) grains found in meteorites. The measurement consists of the time-reversed reaction in inverse kinematics {sup 1}H({sup 21}Ne,{alpha}){sup 18}F at the resonance energy. Using a stable {sup 21}Ne beam, high currents are anticipated requiring a robust hydrogen-containing target. A metal hydride foil would be more apt to withstand the bombardment over a plastic polyethylene target. For this purpose we chose titanium hydride, as the easily produced titanium foils can be reacted with hydrogen to produce the needed targets. Details of the methods of production as well as target characteristics and performance are discussed.

  8. Analysis of transient hydrogen uptake by metal alloy particles

    SciTech Connect

    Zhang, W.; Srinivasan, S.; Ploehn, H.J.

    1996-12-01

    This paper describes a new approach to solving the equations comprising the shrinking core model for diffusion and reaction of a chemical species in a solid spherical particle. The reactant adsorbs on the particle surface, diffuses into the particle`s interior, and reacts with the particle to form a solid product. The shrinking core model assumes a fast reaction rate compared to reactant diffusion so that the reaction is localized in the interfacial zone between the unreacted solid core and the surrounding shell of reacted product. Analytical solutions of the governing conservation equations usually invoke the pseudo-steady state (PSS) approximation which neglects the transient mass accumulation and diffusion-induced convection terms in the continuity equation for the diffusing reactant. However, small particle radii and slow reactant diffusion cast doubt on the validity of the PSS approximation. Dimensional analysis reveals an approximation that is less restrictive than PSS, yet enables a semi-analytical solution for the diffusing reactant distribution and interface velocity. For sufficiently large values of the surface mass fraction of the diffusing reactant, the PSS approximation leads to serious errors in the time dependence of the interface position and fractional conversion. However, the estimate of the surface mass fraction of hydrogen in LaNi{sub 5} particles suggests the validity of the PSS approximation for hydriding of metal alloy particles. The shrinking core model thus enables an estimate of hydrogen diffusivity in metal alloy particles.

  9. Future Propellants for Launch VehiclesMetallic Hydrogen with Water and Hydrocarbon Diluents

    NASA Astrophysics Data System (ADS)

    Cole, J. W.; Silvera, I. F.

    2010-01-01

    Earlier papers have shown that the energy released from recombination of the atomic hydrogen formed when metallic hydrogen is raised above the critical metastabability temperature yields a far greater specific energy and specific impulse than the combustion of hydrogen and oxygen. Experimental efforts continue towards the challenging goal of producing metallic hydrogen in the laboratory. Progress in 2009 has significantly extended the hydrogen high pressure melt line, a path towards metallic hydrogen. The temperature of the recombination reaction of pure metallic hydrogen will be much higher than existing rocket engine materials can withstand. The approach examined here is to dilute the metallic hydrogen, lowering the reaction temperature. Water, hydrocarbons, and liquid molecular hydrogen diluents are shown to provide an attractive specific impulse without exceeding acceptable material technology temperature limits. Analysis of a two-stage mission to the lunar surface with a liquid hydrogen diluted second-stage shows a slight advantage of water and hydrocarbon mixtures as first-stage diluents compared with water only first-stage diluents. Such two-stage in-line vehicles, a little taller than the space shuttle, could deliver very large payloads to the lunar surface or to geosynchronous orbits using the predicted characteristics of diluted metallic hydrogen.

  10. The effect of tensile stress on hydrogen diffusion in metal alloys

    NASA Technical Reports Server (NTRS)

    Danford, M. D.

    1992-01-01

    The effect of tensile stress on hydrogen diffusion has been determined for Type 303 stainless steel, A286 CRES, and Waspaloy and IN100 nickel-base alloys. It was found that hydrogen diffusion coefficients are not significantly affected by stress, while the hydrogen permeabilities are greatly affected in Type 303 stainless steel and A286 CRES (iron-based alloys), but are affected little in Waspaloy (nickel-base) and not affected in all in IN100 (nickel base). These observations might be taken as an indication that hydrogen permeabilities are affected by stress in iron-based alloys, but only slightly affected in nickel-based alloys. However, it is too early to make such a generalization based on the study of only these four alloys.

  11. Hydrogen-environment embrittlement of metals and its control

    NASA Technical Reports Server (NTRS)

    Chandler, W. T.; Walter, R. J.

    1975-01-01

    Types of hydrogen embrittlement are discussed together with characteristics of hydrogen-environment embrittlement, the degree of hydrogen-environment embrittlement of a wide variety of alloys, the effect of hydrogen environments on various properties, (tension, fatigue, creep and fracture mechanics), and the influence of hydrogen exposure parameters on the degree of embrittlement. Design methods for high-pressure hydrogen service and for prevention of hydrogen-environment embrittlement are also covered.

  12. Surface studies of metals after interaction with hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Silver, David Samuel

    1998-12-01

    The objective of this research is to characterize surfaces of metals after interaction with hydrogen isotopes. Iron, which does not readily bond with hydrogen, and palladium, which strongly bonds with hydrogen, were studied. Observations of surfaces are used to determine the nature of their metamorphosis due to such exposures. An experimental study of pure iron foil (99.99%) exposed to a hot, dense hydrogen and argon gas mixture in a ballistic compressor yielded evidence for new structural and compositional changes of the metal due to the exposure. Atomic force microscope (AFM) studies demonstrated surfaces to be highly uneven, where height variations were often 2 mum for many micron-sized regions scanned. An iron foil exposed to argon gases alone revealed unique dendritic patterns but negligible height variations for micron-size scans. A cold rolled single crystal palladium cathode was electrolyzed in a solution of Dsb2O and 15% Hsb2SOsb4 by volume for 12 minutes. The cathode bent toward the anode during electrolysis. Examination of both concave and convex surfaces using the scanning electron microscope (SEM), scanning tunneling microscope (STM), and AFM revealed rimmed craters with faceted crystals inside and multi-textured surfaces. Also pairs of cold rolled polycrystalline palladium cathodes underwent electrolysis for six minutes or less, in Dsb2O and Hsb2O solutions, each solution containing 15% Hsb2SOsb4, by volume. Surface morphologies of the heavy water electrolyzed samples revealed asperities, craters, and nodules, and evidence of recrystallization and crystal planes. After 1.5 years, new AFM studies of the same Pd surfaces exposed to heavy water electrolyte exhibited loose, nanometer-sized particles. However, the surfaces of Pd cathodes exposed to light water electrolyte remained nearly identical to morphologies of foils not electrolyzed, and did not change with time. No surface asperities or loose grains were observed on the latter. Secondary ion mass spectrometry (SIMS) determined the concentrations of the stable six palladium isotopes. A six minute heavy water electrolyzed sample showed inversions of Pdsp{108} with Pdsp{106} and Pdsp{110} with Pdsp{104}, which deviate from their natural abundance. These results support claims made by Fleischmann and Pons that nuclear transformations occur during electrolysis of Pd cathodes in heavy water solutions.

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

    PubMed Central

    Irokawa, Yoshihiro

    2011-01-01

    In this paper, I review my recent results in investigating hydrogen sensors using nitride-based semiconductor diodes, focusing on the interaction mechanism of hydrogen with the devices. Firstly, effects of interfacial modification in the devices on hydrogen detection sensitivity are discussed. Surface defects of GaN under Schottky electrodes do not play a critical role in hydrogen sensing characteristics. However, dielectric layers inserted in metal/semiconductor interfaces are found to cause dramatic changes in hydrogen sensing performance, implying that chemical selectivity to hydrogen could be realized. The capacitance-voltage (CV) characteristics reveal that the work function change in the Schottky metal is not responsible mechanism for hydrogen sensitivity. The interface between the metal and the semiconductor plays a critical role in the interaction of hydrogen with semiconductor devises. Secondly, low-frequency CV characterization is employed to investigate the interaction mechanism of hydrogen with diodes. As a result, it is suggested that the formation of a metal/semiconductor interfacial polarization could be attributed to hydrogen-related dipoles. In addition, using low-frequency CV characterization leads to clear detection of 100 ppm hydrogen even at room temperature where it is hard to detect hydrogen by using conventional current-voltage (IV) characterization, suggesting that low-frequency CV method would be effective in detecting very low hydrogen concentrations. PMID:22346597

  14. Frustrated Lewis pairs: metal-free hydrogen activation and more.

    PubMed

    Stephan, Douglas W; Erker, Gerhard

    2010-01-01

    Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid/Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramolecular combinations of bulky phosphines or amines with strongly electrophilic RB(C(6)F(5))(2) components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H(+)/H(-) pairs (stabilized for example, in the form of the respective phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogenation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alkenes, aldehydes, and a variety of other small molecules, including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chemistry. PMID:20025001

  15. Metal loaded zeolite adsorbents for hydrogen cyanide removal.

    PubMed

    Ning, Ping; Qiu, Juan; Wang, Xueqian; Liu, Wei; Chen, Wei

    2013-04-01

    Metal (Cu, Co, or Zn) loaded ZSM-5 and Y zeolite adsorbents were prepared for the adsorption of hydrogen cyanide (HCN) toxic gas. The results showed that the HCN breakthrough capacity was enhanced significantly when zeolites were loaded with Cu. The physical and chemical properties of the adsorbents that influence the HCN adsorption capacity were analyzed. The maximal HCN breakthrough capacities were about the same for both zeolites at 2.2 mol of HCN/mol of Cu. The Cu2p XPS spectra showed that the possible species present were Cu2O and CuO. The N1s XPS data and FT-IR spectra indicated that CN(-) would be formed in the presence of Cu+/Cu2+ and oxygen gas, and the reaction product could be adsorbed onto Cu/ZSM-5 zeolite more easily than HCN. PMID:23923791

  16. Transport of hydrogen in metals with occupancy dependent trap energies

    SciTech Connect

    Schmid, K. Toussaint, U. von; Schwarz-Selinger, T.

    2014-10-07

    Common diffusion trapping models for modeling hydrogen transport in metals are limited to traps with single de-trapping energies and a saturation occupancy of one. While they are successful in predicting typical mono isotopic ion implantation and thermal degassing experiments, they fail at describing recent experiments on isotope exchange at low temperatures. This paper presents a new modified diffusion trapping model with fill level dependent de-trapping energies that can also explain these new isotope exchange experiments. Density function theory (DFT) calculations predict that even mono vacancies can store between 6 and 12 H atoms with de-trapping energies that depend on the fill level of the mono vacancy. The new fill level dependent diffusion trapping model allows to test these DFT results by bridging the gap in length and time scale between DFT calculations and experiment.

  17. Structure and Bonding in Destabilized Metal Hydrides for Hydrogen Storage.

    NASA Astrophysics Data System (ADS)

    Wu, Hui

    2007-03-01

    Light-metal hydrides possess high hydrogen-storage capacities (> 5 wt.%), but their utility is generally compromised by high thermal stability, rather slow absorption kinetics, and/or problems with reversibility for hydrogen absorption/desorption cycling. There has been great emphasis, particularly in recent years, on attempts to destabilize and otherwise improve the properties of these hydrides by alloying with Si and other elements. We describe here the study of lithium and calcium hydrides alloyed with Si and Ge using ball-milling techniques. The details of the structure and bonding of the Li/Si/H(D), Li/Ge/H(D) and Ca/Si/H(D) systems have been revealed through a combination of neutron and x-ray diffraction, neutron spectroscopy and first-principles calculations. We report the discovery of several new hydride phases, the nature of Si-H bonding in these hydride systems and the effects of amorphization in the Ca/Si/H alloys. The implications of our results for future investigations will be discussed.

  18. The transition to the metallic state in low density hydrogen

    DOE PAGESBeta

    McMinis, Jeremy; Morales, Miguel A.; Ceperley, David M.; Kim, Jeongnim

    2015-11-18

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work we use diffusion quantum Monte Carlo to benchmark the transition between the paramagnetic and anti-ferromagnetic phases of ground state body centered cubic atomic hydrogen. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transitionmore » order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of rs = 2.27(3)a0. As a result, we compare our results to previously reported density functional theory, Hedin s GW approximation, and dynamical mean field theory results.« less

  19. The transition to the metallic state in low density hydrogen

    SciTech Connect

    McMinis, Jeremy; Morales, Miguel A.; Ceperley, David M.; Kim, Jeongnim

    2015-11-18

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work we use diffusion quantum Monte Carlo to benchmark the transition between the paramagnetic and anti-ferromagnetic phases of ground state body centered cubic atomic hydrogen. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of rs = 2.27(3)a0. As a result, we compare our results to previously reported density functional theory, Hedin s GW approximation, and dynamical mean field theory results.

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

    NASA Technical Reports Server (NTRS)

    Danford, M. D.

    1983-01-01

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

  1. Method and Apparatus for the Detection of Hydrogen Using a Metal Alloy

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W. (Inventor)

    1997-01-01

    A hydrogen sensitive metal alloy contains palladium and titanium to provide a larger change in electrical resistance when exposed to the presence of hydrogen. The alloy is deposited on a substrate and a thin film and connected across electrical circuitry to provide a sensor device that can be used for improved sensitivity and accuracy of hydrogen detection.

  2. Photocatalytic properties of colloidal metal sulfides in the decomposition of hydrogen sulfide in aqueous solutions

    SciTech Connect

    Gruzdkov, Yu.A.; Savinov, E.N.; Parmon, V.N.

    1987-03-01

    Investigation has been made of the possibility of using certain metallic sulfides as photocatalysts of the decomposition of hydrogen sulfide into hydrogen and sulfur. It has been shown that photocatalytic activity is possessed by the semiconducting sulfides with the widest forbidden bands. A method is proposed for protecting a photocatalyst from deactivation by the use of an intermediate oxidizer of hydrogen sulfide.

  3. Roles of dynamic metal speciation and membrane permeability in metal flux through lipophilic membranes: general theory and experimental validation with nonlabile complexes.

    PubMed

    Zhang, Zeshi; Buffle, Jacques; van Leeuwen, Herman P

    2007-04-24

    The study of the role of dynamic metal speciation in lipophilic membrane permeability in aqueous solution requires accurate interpretation of experimental data. To meet this goal, a general theory is derived for describing 1:1 metal complex flux, under steady-state and ligand excess conditions, through a permeation liquid membrane (PLM). The theory is applicable to fluxes through any lipophilic membrane. From this theory, fluxes in the three rate-limiting conditions for metal transport are readily derived, corresponding, namely, to (i) diffusion in the source solution, (ii) diffusion in the membrane, and (iii) the chemical kinetics of formation/dissociation of the metal complex in the interfacial reaction layer. The theory enables discussion of the reaction layer concept in a more general frame and also provides unambiguous criteria for the definition of an inert metal complex. The theoretical flux equations for fully labile complexes were validated in a previous paper. The general theory for semi- or nonlabile complexes is validated here by studying the flux of Pb(II) through PLMs in contact with solutions of Pb(II)-NTA and Pb(II)-TMDTA at different pHs and flow rates. PMID:17391055

  4. ACCEPTABILITY ENVELOPE FOR METAL HYDRIDE-BASED HYDROGEN STORAGE SYSTEMS

    SciTech Connect

    Hardy, B.; Corgnale, C.; Tamburello, D.; Garrison, S.; Anton, D.

    2011-07-18

    The design and evaluation of media based hydrogen storage systems requires the use of detailed numerical models and experimental studies, with significant amount of time and monetary investment. Thus a scoping tool, referred to as the Acceptability Envelope, was developed to screen preliminary candidate media and storage vessel designs, identifying the range of chemical, physical and geometrical parameters for the coupled media and storage vessel system that allow it to meet performance targets. The model which underpins the analysis allows simplifying the storage system, thus resulting in one input-one output scheme, by grouping of selected quantities. Two cases have been analyzed and results are presented here. In the first application the DOE technical targets (Year 2010, Year 2015 and Ultimate) are used to determine the range of parameters required for the metal hydride media and storage vessel. In the second case the most promising metal hydrides available are compared, highlighting the potential of storage systems, utilizing them, to achieve 40% of the 2010 DOE technical target. Results show that systems based on Li-Mg media have the best potential to attain these performance targets.

  5. Chemical bonding of hydrogen molecules to transition metal complexes

    SciTech Connect

    Kubas, G.J.

    1990-01-01

    The complex W(CO){sub 3}(PR{sub 3}){sub 2}(H{sub 2}) (CO = carbonyl; PR{sub 3} = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H{sub 2} exchanges easily with D{sub 2}. This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H{sub 2} bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H{sub 2})(R{sub 2}PCH{sub 2}CH{sub 2}PR{sub 2}){sub 2} were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig.

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

    PubMed

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

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating. PMID:25017188

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  8. Transition metal activation and functionalization of carbon-hydrogen bonds

    SciTech Connect

    Jones, W.D.

    1990-07-01

    This project is directed toward the continued investigation of the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers. The project is also directed toward the conversion of hydrocarbons into functionalized products of potential use to chemical industry. In the past year, advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalized of hydrocarbons. Major advanced that have been made include: (1) We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds of arenes upon photolysis. (2) We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. (3) We have begun to examine the reactions of rhodium pyrazolylborates for isonitrile functionalization of C-H bonds. (4) We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more faciley than reductive elimination of H{sub 12}. (5) We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation.

  9. Transition metal activation and functionalization of carbon-hydrogen bonds

    SciTech Connect

    Jones, W.D.

    1991-06-01

    This project is directed towards the continued investigation of the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers. The project is also directed towards the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. In the past two years, advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. Major advances that have been made include: (1) We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds of arenes upon photolysis. (2) We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. (3) We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. (4) We have completed studies of the reactions of (C{sub 5}Me{sub 5)}Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. (5) We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion. 43 refs., 9 figs., 4 tabs.

  10. Mechanism for high hydrogen storage capacity on metal-coated carbon nanotubes: A first principle analysis

    SciTech Connect

    Lu, Jinlian; Xiao, Hong; Cao, Juexian

    2012-12-15

    The hydrogen adsorption and binding mechanism on metals (Ca, Sc, Ti and V) decorated single walled carbon nanotubes (SWCNTs) are investigated using first principle calculations. Our results show that those metals coated on SWCNTs can uptake over 8 wt% hydrogen molecules with binding energy range -0.2--0.6 eV, promising potential high density hydrogen storage material. The binding mechanism is originated from the electrostatic Coulomb attraction, which is induced by the electric field due to the charge transfer from metal 4s to 3d. Moreover, we found that the interaction between the H{sub 2}-H{sub 2} further lowers the binding energy. - Graphical abstract: Five hydrogen molecules bound to individual Ca decorated (8, 0) SWCNT : a potential hydrogen-storage material. Highlights: Black-Right-Pointing-Pointer Each transition metal atom can adsorb more than four hydrogen molecules. Black-Right-Pointing-Pointer The interation between metal and hydrogen molecule is electrostatic coulomb attraction. Black-Right-Pointing-Pointer The electric field is induced by the charge transfer from metal 4s to metal 3d. Black-Right-Pointing-Pointer The adsorbed hydrogen molecules which form supermolecule can further lower the binding energy.

  11. The permeability of silicone rubber to metal compounds: relevance to implanted devices.

    PubMed

    Donaldson, Nick; Baviskar, Preeti; Cunningham, Jim; Wilson, Darren

    2012-03-01

    Most implanted electrical devices use encapsulant as insulation. The encapsulant may remain functional for many years, bonded to the metallic surfaces, but eventually become partly detached allowing corrosion to occur. To understand whether the corrosion products will cause toxic effects, we need to know how quickly they will permeate through the encapsulant. In these experiments, silicone capsules (the encapsulant) containing metal compounds were left in jars of initially pure water for 6 months, and the concentration of the metal in the water was measured. The amount of metal depended on the type of compound; for the organometallic compounds tested, permeation was very rapid. However, for most of the other compounds, whether oxides or salts, the amount of metal was below the control level and therefore could have been the result of contamination. These compounds were tin sulfate and oxide (<10²), lead nitrate and oxide (<10²), copper sulfate (<10³), and nitrates of bismuth (<10¹), chrome (<10²), nickel (<10³) and zinc (<10²). The numbers in brackets are the maximum mass (ng) of permeated metal after 6 months. Three silver compounds were tested but without proper controls; however, the amount of permeated silver appeared to be low: silver oxide (1.3 × 10²), silver nitrate (6.3 × 10¹), and silver chloride (6 × 10⁰). The resolution of this method is limited by contamination that is detected by control capsules. The conclusion is that compounds that are likely corrosion products permeate through silicone encapsulant at a low rate and seem unlikely to cause toxic effects. PMID:22213669

  12. Thickness dependence of hydrogen permeability for Ni-BaCe{sub 0.8}Y{sub 0.2}O{sub 3-{delta}}.

    SciTech Connect

    Song, S.-J.; Moon, J.-H.; Lee, T. H.; Dorris, S. E.; Balachandran, U.; Energy Systems; Chonnam National Univ.

    2008-10-01

    The hydrogen separation properties and thickness dependence of the hydrogen flux for Ni-BCY membranes, containing a proton-conductor (BaCe{sub 0.8}Y{sub 0.2}O{sub 3-{alpha}}, i.e., BCY) and an electron-conductor (Ni metal), were studied as a function of temperature in the thickness range of 0.08-1.16 mm. Feed gas was composed of 3.8% H{sub 2} balanced with He (pH{sub 2}O = 0.03 atm) gas and sweep gas contained 100 ppm hydrogen balanced with nitrogen. The hydrogen permeation flux due to ambipolar diffusion dominates over the entire experimental temperature range, but the hydrogen permeation flux through the Ni-metal increases with temperature due to its endothermic hydrogen solubility. The hydrogen flux through the Ni-BCY membranes is inversely proportional to the thickness, indicating that bulk diffusion is the rate limiting step down to a thickness of 80 {micro}m. For thicker (> 640 {micro}m) membranes, the flux decreases monotonically as the temperature increases up to 900 C, whereas the flux for thinner (< 200 {micro}m) membranes increases as temperature increases up to {approx} 750 C and then remains nearly constant as the temperature is further increased.

  13. Enhanced chitosan beads-supported Fe(0)-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers.

    PubMed

    Liu, Tingyi; Yang, Xi; Wang, Zhong-Liang; Yan, Xiaoxing

    2013-11-01

    The removal of heavy metals from electroplating wastewater is a matter of paramount importance due to their high toxicity causing major environmental pollution problems. Nanoscale zero-valent iron (NZVI) became more effective to remove heavy metals from electroplating wastewater when enhanced chitosan (CS) beads were introduced as a support material in permeable reactive barriers (PRBs). The removal rate of Cr (VI) decreased with an increase of pH and initial Cr (VI) concentration. However, the removal rates of Cu (II), Cd (II) and Pb (II) increased with an increase of pH while decreased with an increase of their initial concentrations. The initial concentrations of heavy metals showed an effect on their removal sequence. Scanning electron microscope images showed that CS-NZVI beads enhanced by ethylene glycol diglycidyl ether (EGDE) had a loose and porous surface with a nucleus-shell structure. The pore size of the nucleus ranged from 19.2 to 138.6 ?m with an average aperture size of around 58.6 ?m. The shell showed a tube structure and electroplating wastewaters may reach NZVI through these tubes. X-ray photoelectron spectroscope (XPS) demonstrated that the reduction of Cr (VI) to Cr (III) was complete in less than 2 h. Cu (II) and Pb (II) were removed via predominant reduction and auxiliary adsorption. However, main adsorption and auxiliary reduction worked for the removal of Cd (II). The removal rate of total Cr, Cu (II), Cd (II) and Pb (II) from actual electroplating wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively. The findings revealed that EGDE-CS-NZVI-beads PRBs had the capacity to remediate actual electroplating wastewater and may become an effective and promising technology for in situ remediation of heavy metals. PMID:24075723

  14. Chemomechanical Origin of Hydrogen Trapping at Grain Boundaries in fcc Metals.

    PubMed

    Zhou, Xiao; Marchand, Daniel; McDowell, David L; Zhu, Ting; Song, Jun

    2016-02-19

    Hydrogen embrittlement of metals is widely observed, but its atomistic origins remain little understood and much debated. Combining a unique identification of interstitial sites through polyhedral tessellation and first-principles calculations, we study hydrogen adsorption at grain boundaries in a variety of face-centered cubic metals of Ni, Cu, γ-Fe, and Pd. We discover the chemomechanical origin of the variation of adsorption energetics for interstitial hydrogen at grain boundaries. A general chemomechanical formula is established to provide accurate assessments of hydrogen trapping and segregation energetics at grain boundaries, and it also offers direct explanations for certain experimental observations. The present study deepens our mechanistic understanding of the role of grain boundaries in hydrogen embrittlement and points to a viable path towards predictive microstructure engineering against hydrogen embrittlement in structural metals. PMID:26943544

  15. Chemomechanical Origin of Hydrogen Trapping at Grain Boundaries in fcc Metals

    NASA Astrophysics Data System (ADS)

    Zhou, Xiao; Marchand, Daniel; McDowell, David L.; Zhu, Ting; Song, Jun

    2016-02-01

    Hydrogen embrittlement of metals is widely observed, but its atomistic origins remain little understood and much debated. Combining a unique identification of interstitial sites through polyhedral tessellation and first-principles calculations, we study hydrogen adsorption at grain boundaries in a variety of face-centered cubic metals of Ni, Cu, γ -Fe , and Pd. We discover the chemomechanical origin of the variation of adsorption energetics for interstitial hydrogen at grain boundaries. A general chemomechanical formula is established to provide accurate assessments of hydrogen trapping and segregation energetics at grain boundaries, and it also offers direct explanations for certain experimental observations. The present study deepens our mechanistic understanding of the role of grain boundaries in hydrogen embrittlement and points to a viable path towards predictive microstructure engineering against hydrogen embrittlement in structural metals.

  16. Miniaturized metal (metal alloy)/ PdO.sub.x/SiC hydrogen and hydrocarbon gas sensors

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor); Lukco, Dorothy (Inventor)

    2011-01-01

    A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO.sub.x ). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600.degree. C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sized sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

  17. Miniaturized Metal (Metal Alloy)/PdO(x)/SiC Hydrogen and Hydrocarbon Gas Sensors

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor); Lukco, Dorothy (Inventor)

    2008-01-01

    A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO(x)). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600 C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sided sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

  18. Miniaturized metal (metal alloy)/ PdO.sub.x/SiC hydrogen and hydrocarbon gas sensors

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor); Lukco, Dorothy (Inventor)

    2008-01-01

    A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO.sub.x). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600.degree. C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sized sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

  19. Hydrogen absorption induced metal deposition on palladium and palladium-alloy particles

    DOEpatents

    Wang, Jia X. (East Setauket, NY); Adzic, Radoslav R. (East Setauket, NY)

    2009-03-24

    The present invention relates to methods for producing metal-coated palladium or palladium-alloy particles. The method includes contacting hydrogen-absorbed palladium or palladium-alloy particles with one or more metal salts to produce a sub-monoatomic or monoatomic metal- or metal-alloy coating on the surface of the hydrogen-absorbed palladium or palladium-alloy particles. The invention also relates to methods for producing catalysts and methods for producing electrical energy using the metal-coated palladium or palladium-alloy particles of the present invention.

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

    NASA Astrophysics Data System (ADS)

    Musket, R. G.

    1988-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Musket, R. G.

    1989-04-01

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

  2. Hydrogen Adsorption, Absorption and Diffusion on and in Transition Metal Surfaces: A DFT Study

    SciTech Connect

    Ferrin, Peter A.; Kandoi, Shampa; Nilekar, Anand U.; Mavrikakis, Manos

    2012-01-04

    Periodic, self-consistent DFT-GGA(PW91) calculations are used to study the interaction of hydrogen with different facets of seventeen transition metals—the (100) and (111) facets of face-centered cubic (fcc) metals, the (0001) facet of hexagonal-close packed (hcp) metals, and the (100) and (110) facets of body-centered cubic (bcc) metals. Calculated geometries and binding energies for surface and subsurface hydrogen are reported and are, in general, in good agreement with both previous modeling studies and experimental data. There are significant differences between the binding on the close-packed and more open (100) facets of the same metal. Geometries of subsurface hydrogen on different facets of the same metal are generally similar; however, binding energies of hydrogen in the subsurface of the different facets studied showed significant variation. Formation of surface hydrogen is exothermic with respect to gas-phase H₂ on all metals studied with the exception of Ag and Au. For each metal studied, hydrogen in its preferred subsurface state is always less stable than its preferred surface state. The magnitude of the activation energy for hydrogen diffusion from the surface layer into the first subsurface layer is dominated by the difference in the thermodynamic stability of these two states. Diffusion from the first subsurface layer to one layer further into the bulk does not generally have a large thermodynamic barrier but still has a moderate kinetic barrier. Despite the proximity to the metal surface, the activation energy for hydrogen diffusion from the first to the second subsurface layer is generally similar to experimentally-determined activation energies for bulk diffusion found in the literature. There are also some significant differences in the activation energy for hydrogen diffusion into the bulk through different facets of the same metal.

  3. Heat energy from hydrogen-metal nuclear interactions

    NASA Astrophysics Data System (ADS)

    Hadjichristos, John; Gluck, Peter

    2013-11-01

    The discovery of the Fleischmann-Pons Effect in 1989, a promise of an abundant, cheap and clean energy source was premature in the sense that theoretical knowledge, relative technologies and the experimental tools necessary for understanding and for scale-up still were not available. Therefore the field, despite efforts and diversification remained quasi-stagnant, the effect (a scientific certainty) being of low intensity leading to mainstream science to reject the phenomenon and not supporting its study. Recently however, the situation has changed, a new paradigm is in statunascendi and the obstacles are systematically removed by innovative approaches. Defkalion, a Greek company (that recently moved in Canada for faster progress) has elaborated an original technology for the Ni-H system [1-3]. It is about the activation of hydrogen and creation of nuclear active nano-cavities in the metal through a multi-stage interaction, materializing some recent breakthrough announcements in nanotechnology, superconductivity, plasma physics, astrophysics and material science. A pre-industrial generator and a novel mass-spectrometry instrumentations were created. Simultaneously, a meta-theory of phenomena was sketched in collaboration with Prof. Y. Kim (Purdue U).

  4. Oxidative Dissolution of Nickel Metal in Hydrogenated Hydrothermal Solutions

    SciTech Connect

    Ziemniak, S. E.; Guilmette, P. A.; Turcotte, R. A.; Tunison, H. M.

    2007-03-27

    A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of metallic nickel in hydrogenated ammonia and sodium hydroxide solutions between 175 and 315 C. The solubility measurements were interpreted by means of an oxidative dissolution reaction followed by a sequence of Ni(II) ion hydrolysis reactions: Ni(s) + 2H+(aq) = Ni2+(aq) + H2(g) and Ni{sup 2+}(aq) + nH{sub 2}O = Ni(OH){sub n}{sup 2-n}(aq) + nH{sup +}(aq) where n = 1 and 2. Gibbs energies associated with these reaction equilibria were determined from a least-squares analysis of the data. The extracted thermochemical properties ({Delta}fG{sup 0}, {Delta}fH{sup 0} and S{sup 0}) for Ni2{sup +}(aq), Ni(OH){sup +}(aq) and Ni(OH){sub 2}(aq) were found to be consistent with those determined in a previous solubility study of NiO/Ni(OH){sub 2} conducted in our laboratory. The thermodynamic basis of the Ni/NiO phase boundary in aqueous solutions is examined to show that Ni(s) is stable relative to NiO(s) in solutions saturated at 25 C with 1 atm H{sub 2} for temperatures below 309 C.

  5. Heat energy from hydrogen-metal nuclear interactions

    SciTech Connect

    Hadjichristos, John; Gluck, Peter

    2013-11-13

    The discovery of the Fleischmann-Pons Effect in 1989, a promise of an abundant, cheap and clean energy source was premature in the sense that theoretical knowledge, relative technologies and the experimental tools necessary for understanding and for scale-up still were not available. Therefore the field, despite efforts and diversification remained quasi-stagnant, the effect (a scientific certainty) being of low intensity leading to mainstream science to reject the phenomenon and not supporting its study. Recently however, the situation has changed, a new paradigm is in statunascendi and the obstacles are systematically removed by innovative approaches. Defkalion, a Greek company (that recently moved in Canada for faster progress) has elaborated an original technology for the Ni-H system [1-3]. It is about the activation of hydrogen and creation of nuclear active nano-cavities in the metal through a multi-stage interaction, materializing some recent breakthrough announcements in nanotechnology, superconductivity, plasma physics, astrophysics and material science. A pre-industrial generator and a novel mass-spectrometry instrumentations were created. Simultaneously, a meta-theory of phenomena was sketched in collaboration with Prof. Y. Kim (Purdue U)

  6. Effect of transition-metal additives on hydrogen desorption kinetics of MgH2

    NASA Astrophysics Data System (ADS)

    Roy, Anindya; Janotti, Anderson; Van de Walle, Chris G.

    2013-01-01

    Using first-principles calculations, we study the effect of transition-metal additives (Ti, Fe, Co, and Ni) on the rate of hydrogen desorption in MgH2. The presence of large concentrations of transition-metal impurities causes the Fermi level to shift according to the position of the transition-metal acceptor/donor levels in the band gap. This shift can lower the formation energy of native defects and increase their concentration. The resulting higher rates of hydrogen desorption enhance the prospect of MgH2 as a solid-state hydrogen-storage material.

  7. Hydrogen Adsorption by Alkali Metal Graphite Intercalation Compounds

    NASA Astrophysics Data System (ADS)

    Purewal, Justin

    Adsorption occurs whenever a solid surface is exposed to a gas or liquid, and is characterized by an increase in fluid density near the interface. Adsorbents have drawn attention in the current effort to engineer materials that store hydrogen at high densities within moderate temperature and pressure regimes. Carbon adsorbents are a logical choice as a storage material due to their low costs and large surface areas. Unfortunately, carbon adsorbents suffer from a low binding enthalpy for H2 (about 5 kJ mol-1), well below the 15 to 18 kJ mol-1) that is considered optimal for hydrogen storage systems. Binding interactions can be increased by the following methods: (1) adjusting the graphite interplanar separation with a pillared structure, and (2) introducing dopant species that interact with H2 molecules by strong electrostatic forces. Graphite intercalation compounds are a class of materials that contain both pillared structures and chemical dopants, making them an excellent model system for studying the fundamentals of hydrogen adsorption in nanostructured carbons. Pressure-composition-temperature diagrams of the MC24(H 2)x graphite intercalation compounds were measured for M = (K, Rb, Cs). Adsorption enthalpies were measured as a function of H2 concentration. Notably, CsC24 had an average adsorption enthalpy of 14.9 kJ mol-1), nearly three times larger than that of pristine graphite. The adsorption enthalpies were found to be positively correlated with the alkali metal size. Adsorption capacities were negatively correlated with the size of the alkali metal. The rate of adsorption is reduced at large H2 compositions, due to the effects of site-blocking and correlation on the H2 diffusion. The strong binding interaction and pronounced molecular-sieving behavior of KC24 is likely to obstruct the translational diffusion of adsorbed H2 molecules. In this work, the diffusion of H2 adsorbed in KC24 was studied by quasielastic neutron scattering measurements and molecular dynamics simulations. As predicted, the rate of diffusion in KC24 is over an order of magnitude slower than in other carbon adsorbents (e.g. carbon nanotubes, nanohorns and carbon blacks). It is similar in magnitude to the rate of H2 diffusion in zeolites with molecular-sized cavities. This suggests that H2 diffusion in adsorbents is influenced very strongly by the pore geometry. The H2 diffusion process in KC24 contains at least two distinct jump frequencies. Bound states of adsorbed H2 in KC24 were investigated by inelastic neutron scattering measurements and density functional theory calculations. Spectral peaks in the neutron energy loss range of 5 meV to 45 meV were observed for the first time. These peaks were interpreted as single- and multi-excitation transitions of the H2 phonon and rotational modes. The rotational barrier for H2 molecules is many times larger in KC24 than in other carbon adsorbents, apparently due to the confinement of the molecules between closely-spaced graphitic layers. Evidence was found for the existence of at least three H2 sorption sites in KC24, each with a distinctive rotational barrier.

  8. Polymerization effect of electrolytes on hydrogen-bonding cryoprotectants: ion-dipole interactions between metal ions and glycerol.

    PubMed

    Weng, Lindong; Elliott, Gloria D

    2014-12-11

    Protectants which are cell membrane permeable, such as glycerol, have been used effectively in the cryopreservation field for a number of decades, for both slow cooling and vitrification applications. In the latter case, the glass transition temperature (Tg) of the vitrification composition is key to its application, dictating the ultimate storage conditions. It has been observed that the addition of some electrolytes to glycerol, such as MgCl2, could elevate the Tg of the mixture, thus potentially providing more storage condition flexibility. The microscopic mechanisms that give rise to the Tg-enhancing behavior of these electrolytes are not yet well understood. The current study focuses on molecular dynamics simulation of glycerol mixed with a variety of metal chlorides (i.e., NaCl, KCl, MgCl2, and CaCl2), covering a temperature range that spans both the liquid and glassy states. The characteristics of the ion-dipole interactions between metal cations and hydroxyl groups of glycerol were analyzed. The interruption of the original hydrogen-bonding network among glycerol molecules by the addition of ions was also investigated in the context of hydrogen-bonding quantity and lifetime. Divalent metal cations were found to significantly increase the Tg by strengthening the interacting network in the electrolyte/glycerol mixture via strong cation-dipole attractions. In contrast, monovalent cations increased the Tg insignificantly, as the cation-dipole attraction was only slightly stronger than the original hydrogen-bonding network among glycerol molecules. The precursor of crystallization of NaCl and KCl was also observed in these compositions, potentially contributing to weak Tg-enhancing ability. The Tg-enhancing mechanisms elucidated in this study suggest a structure-enhancing role for divalent ions that could be of benefit in the design of protective formulations for biopreservation purposes. PMID:25405831

  9. Polymerization Effect of Electrolytes on Hydrogen-Bonding Cryoprotectants: IonDipole Interactions between Metal Ions and Glycerol

    PubMed Central

    2015-01-01

    Protectants which are cell membrane permeable, such as glycerol, have been used effectively in the cryopreservation field for a number of decades, for both slow cooling and vitrification applications. In the latter case, the glass transition temperature (Tg) of the vitrification composition is key to its application, dictating the ultimate storage conditions. It has been observed that the addition of some electrolytes to glycerol, such as MgCl2, could elevate the Tg of the mixture, thus potentially providing more storage condition flexibility. The microscopic mechanisms that give rise to the Tg-enhancing behavior of these electrolytes are not yet well understood. The current study focuses on molecular dynamics simulation of glycerol mixed with a variety of metal chlorides (i.e., NaCl, KCl, MgCl2, and CaCl2), covering a temperature range that spans both the liquid and glassy states. The characteristics of the iondipole interactions between metal cations and hydroxyl groups of glycerol were analyzed. The interruption of the original hydrogen-bonding network among glycerol molecules by the addition of ions was also investigated in the context of hydrogen-bonding quantity and lifetime. Divalent metal cations were found to significantly increase the Tg by strengthening the interacting network in the electrolyte/glycerol mixture via strong cationdipole attractions. In contrast, monovalent cations increased the Tg insignificantly, as the cationdipole attraction was only slightly stronger than the original hydrogen-bonding network among glycerol molecules. The precursor of crystallization of NaCl and KCl was also observed in these compositions, potentially contributing to weak Tg-enhancing ability. The Tg-enhancing mechanisms elucidated in this study suggest a structure-enhancing role for divalent ions that could be of benefit in the design of protective formulations for biopreservation purposes. PMID:25405831

  10. Transition metal activation and functionalization of carbon-hydrogen bonds

    SciTech Connect

    Jones, W.D.

    1992-06-01

    We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.

  11. Hydrogen storage in the form of metal hydrides

    NASA Technical Reports Server (NTRS)

    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.

  12. Optimization of neutron tomography for rapid hydrogen concentration inspection of metal castings

    SciTech Connect

    Gibbons, M. R., LLNL

    1998-02-03

    Hydrogen embrittlement describes a group of phenomena leading to the degradation of metal alloy properties. The hydrogen concentration in the alloy can be used as an indicator for the onset of embrittlement. A neutron tomography system has been optimized to perform nondestructive detection of hydrogen concentration in titanium aircraft engine compressor blades. Preprocessing of back projection images and postprocessing of tomographic reconstructions are used to achieve hydrogen concentration sensitivity below 200 ppm weight. This paper emphasizes the postprocessing techniques which allow automated reporting of hydrogen concentration.

  13. First principles study of hydrogen storage in non-transition metal decorated graphitic materials

    NASA Astrophysics Data System (ADS)

    Kim, Gyubong; Park, Noejung; Jhi, Seung-Hoon

    2008-03-01

    Hydrogen has been considered an ideal material that can replace fossil-based fuels as its byproduct is simply water without emitting green house gases. Recently, transition metal (TM)- dispersed porous materials have been suggested as plausible candidates for hydrogen storages that possess optimal hydrogen binding characteristics. A serious problem in this approach is that TM atoms tend to aggregate instead of being atomistically dispersed, which results in the deterioration of hydrogen uptake. Here we study the hydrogen adsorption on non-transition metal (NTM) atoms dispersed on graphene using ab initio methods. We observe that the clustering energy of NTM atoms is much smaller than that of TM atoms, which indicates that NTM can be almost free of clustering on graphene. We also study hydrogen adsorption on those NTM atoms to find comparable storage capacity to that in TM dispersed graphene.

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

    PubMed

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

    2015-03-01

    Stabilization of metal nanoparticles (MNPs) without re-aggregation is a major challenge. An unprecedented strategy is developed for achieving high dispersion of copper(0) or palladium(0) on montmorillonite-supported diethanolamine or thioglycerol. This results in novel metal-inorganic-organic matrices (MIOM) that readily capture hydrogen at ambient conditions, with easy release under air stream. Hydrogen retention appears to involve mainly physical interactions, slightly stronger on thioglycerol-based MIOM (S-MIOM). Thermal enhancement of desorption suggests also a contribution of chemical interactions. The increase of hydrogen uptake with prolonged contact times arises from diffusion hindrance, which appears to be beneficial by favoring hydrogen entrapment. Even with compact structures, MIOMs act as efficient sorbents with much higher efficiency factor (1.14-1.17?mmol?H?2?m(-2)) than many other sophisticated adsorbents reported in the literature. This opens new prospects for hydrogen storage and potential applications in microfluidic hydrogenation reactions. PMID:25663131

  15. Metal Oxide Nanomaterials for Solar Energy to Hydrogen Fuel Conversion

    NASA Astrophysics Data System (ADS)

    Sabio, Erwin Murillo

    Photoactive metal oxide nanomaterials enable full or partial water splitting by reducing water to hydrogen and oxidizing water into oxygen through transfer of photogenerated electrons and holes, respectively, upon absorption of light of certain frequencies. Scanning Transmission Electron Microscopy (STEM) is one of the useful instruments to study these materials through observation of their atomic structures using high resolution imaging and through chemical analyses using complementary analytical techniques. Combinations of z-contrast imaging, selected area electron diffraction (SAED), electron dispersive x-ray spectroscopy (EDX), and electron energy loss spectroscopy (EELS) were used to elucidate the structures of IrO2, H2Ti4O 9, H2K2Nb6O17 and WO 3 photocatalysts. STEM techniques were also employed to observe the reduction of V2O5 nanoribbons into photoactive VO 2 and to monitor the effect of sonication on the size and crystallinity of TBACa2Nb3O10 (TBA = tetrabutylammonium) nano sheets. Aberration-corrected STEM equipped with a fluid stage was utilized to examine water catalysis by TBACa2Nb3O10 in situ under the electron beam. Phenomena associated with calcium niobate catalysis such as photodeposition of Pt and IrO2 co-catalysts and the surface poisoning with Ag particles during water oxidation were observed in real time. Formation of gas bubbles during water reduction was also detected as it occurs using dark field imaging and EELS. Electron microscopy was also employed to probe charge separation and distribution of redox-active sites on photolabeled TBACa2Nb 3O10. The sizes, shapes, and particle densities vary with the precursor concentration and the presence of sacrificial agents. Photogenerated electrons and holes were shown to be accessible throughout the nanosheets, without evidence for spatial charge separation across the sheet. To measure the relative catalytic activities of multiple photocatalysts, a comparative quantum efficiency (QE) study was carried out on the H 2Ti4O9 nanobelts, H2K2Nb 6O17 nanoscrolls, PA2K2Nb6O 17 (PA = propylammonium) and TBACa2Nb3O10 nanosheets, and their platinated counterparts. Hydrogen and oxygen evolved upon irradiation with a Xe lamp were measured using gas chromatography (GC). The QEs of these catalysts were found to be dependent on the quasi-Fermi levels (QFLs) and the mobility of the charge carriers as measured by surface photovoltage spectroscopy (SPV). A similar photocatalytic study was employed to measure the effects of exfoliation, sacrificial charge donors, presence of co-catalysts, and co-catalyst deposition conditions on the TBACa2Nb3O10 nanosheets. Factorial analysis on the hydrogen and oxygen evolution results showed the degree of dependence of catalytic activity on these factors. High resolution STEM and cyclic voltammetry showed the structural and electronic features of the nanosheets that give rise to the observed effects of the factors studied.

  16. Metal-nonmetal transition in dense hydrogen plasma

    SciTech Connect

    Reinholz, H.; Redmer, R.; Nagel, S.

    1995-12-31

    A quantum statistical approach to the equation of state and the transport properties of partially ionized hydrogen plasma is utilized to determine the region of thermodynamic instability and the location of the metal-nonmetal transition. The elementary electrons e and protons p as well as two-particle states are treated correctly within a physical picture. The influence of higher clusters such as dimers H{sub 2} and molecular ions H{sub 2}{sup +}, however, is studied within the chemical picture. For this, the two-particle partition function is calculated by means of an improved Beth-Uhlenbeck formula. Nonideality corrections due to the interaction between the various species are considered in the respective laws of mass action. A thermodynamic instability is found for the strongly coupled plasma domain. The critical point at T{sub c} = 16.5 x 10{sup 3} K, {wp}{sub c} = 0.42 g/cm{sup 3}, and p{sub c} = 57 GPa coincides with earlier results for this hypothetical plasma phase transition. Near the instability region, all species have strongly varying concentrations which indicates the significant influence of nonideality corrections on the thermodynamic functions. The transport properties are studied from the weakly coupled, nondegenerate region up to strongly coupled, degenerate domain. Such a universal approach which includes the Spitzer as well as the Ziman theory as limiting cases can be formulated within linear response theory. Again, two-particle correlations have been accounted for by the correct quantum cross sections for electron scattering at ions and free electrons. Electron scattering at neutral atoms was considered on T matrix level with respect to an effective optical potential. Strong ion-ion correlations are of special importance at high densities. The respective ion-ion structure factor was determined numerically within the HNC scheme, taking into account local-field corrections to the screening function of the effective ion-ion interaction potential.

  17. Optical studies of hydrogen above 200 gigapascals - Evidence for metallization by band overlap

    NASA Technical Reports Server (NTRS)

    Mao, N. K.; Hemley, R. J.

    1989-01-01

    Direct optical observations of solid hydrogen to pressures in the 250-gigapascal range at 77 K are reported. Hydrogen samples appear nearly opaque at the maximum pressures. Measurements of absorption and Raman spectra provide evidence that electronic excitations in the visible region begin at about 200 gigapascals. The optical data are consistent with a band-overlap mechanism of metallization.

  18. Discovery of spontaneous deformation of Pd metal during hydrogen absorption/desorption cycles

    PubMed Central

    Yamazaki, Toshimitsu; Sato, Masaharu; Itoh, Satoshi

    2009-01-01

    A drastic deformation was observed in Pd metal of various shapes after hydrogen absorption and desorption cycles at 150 °C at a gas pressure of 1–5 MPa. All of the phenomena observed indicate that some strong internal force is induced spontaneously during hydrogen absorption/desorption cycles to produce a collective deformation so as to minimize the surface. PMID:19444010

  19. Combinatorial preparation and infrared screening of hydrogen sorbing metal alloys

    NASA Astrophysics Data System (ADS)

    Olk, C. H.; Tibbetts, G. G.; Simon, D.; Moleski, J. J.

    2003-07-01

    We introduce the use of thin-film combinatorial methods to synthesize Mg-based hydrogen storage alloys and demonstrate the use of spatially resolved infrared imaging as a high throughput hydrogen storage candidate screening technique. Using a combination of pulsed laser deposition and magnetron sputtering, multicompositional samples were produced for hydrogen sorption studies. Analysis is presented of a sample that consists of 16 separate Mg-Ni-Fe ternary pads and 32 Mg-Ni or Mg-Fe binary pads. Hydrogen sorption related emissivity changes observed indicate a substantial decrease in hydriding temperatures, which sensitively depends on composition.

  20. Highly mobile and reactive state of hydrogen in metal oxide semiconductors at room temperature

    PubMed Central

    Chen, Wan Ping; He, Ke Feng; Wang, Yu; Chan, Helen Lai Wah; Yan, Zijie

    2013-01-01

    Hydrogen in metal oxides usually strongly associates with a neighboring oxygen ion through an O-H bond and thus displays a high stability. Here we report a novel state of hydrogen with unusually high mobility and reactivity in metal oxides at room temperature. We show that freshly doped hydrogen in Nb2O5 and WO3 polycrystals via electrochemical hydrogenation can reduce Cu2+ ions into Cu0 if the polycrystals are immersed in a CuSO4 solution, while this would not happen if the hydrogenated polycrystals have been placed in air for several hours before the immersion. Time-dependent studies of electrochemically hydrogenated rutile single crystals reveal two distinct states of hydrogen: one as protons covalently bonded to oxygen ions, while the other one is highly unstable with a lifetime of just a few hours. Observation of this mobile and reactive state of hydrogen will provide new insight into numerous moderate and low temperature interactions between metal oxides and hydrogen. PMID:24193143

  1. Energy decomposition analysis of cation-?, metal ion-lone pair, hydrogen bonded, charge-assisted hydrogen bonded, and ?-? interactions.

    PubMed

    Sharma, Bhaskar; Srivastava, Hemant Kumar; Gayatri, Gaddamanugu; Sastry, Garikapati Narahari

    2015-03-30

    This study probes the nature of noncovalent interactions, such as cation-?, metal ion-lone pair (M-LP), hydrogen bonding (HB), charge-assisted hydrogen bonding (CAHB), and ?-? interactions, using energy decomposition schemes-density functional theory (DFT)-symmetry-adapted perturbation theory and reduced variational space. Among cation-? complexes, the polarization and electrostatic components are the major contributors to the interaction energy (IE) for metal ion-? complexes, while for onium ion-? complexes (NH4+, PH4+, OH3+, and SH3+) the dispersion component is prominent. For M-LP complexes, the electrostatic component contributes more to the IE except the dicationic metal ion complexes with H2 S and PH3 where the polarization component dominates. Although electrostatic component dominates for the HB and CAHB complexes, dispersion is predominant in ?-? complexes. PMID:25581071

  2. Improved retort for cleaning metal powders with hydrogen

    NASA Technical Reports Server (NTRS)

    Arias, A.

    1969-01-01

    Improved cleaning retort produces uniform temperature distribution in the heated zone and minimizes hydrogen channeling through the powder bed. Retort can be used for nonmetallic powders, sintering in a reducing atmosphere, and for cleaning powders in reduction atmospheres other than hydrogen.

  3. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene.

    PubMed

    Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas; Srensen, Rasmus Z; Christensen, Claus H; Nrskov, Jens K

    2008-06-01

    The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts (often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional calculations were performed that identified relations in heats of adsorption of hydrocarbon molecules and fragments on metal surfaces. This analysis not only verified the facility of known catalysts but identified nickel-zinc alloys as alternatives. Experimental studies demonstrated that these alloys dispersed on an oxide support were selective for acetylene hydrogenation at low pressures. PMID:18535238

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

    NASA Astrophysics Data System (ADS)

    Patki, Gauri Dilip

    Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the 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.

  5. Aqueous-phase hydrogenation of acetic acid over transition metal catalysts

    SciTech Connect

    Olcay, Hakan; Xu, Lijun; Xu, Ye; Huber, George

    2010-01-01

    Catalytic hydrogenation of acetic acid to ethanol has been carried out in aqueous phase on several metals, with ruthenium being the most active and selective. DFT calculations suggest that the initial CO bond scission yielding acetyl is the key step and that the intrinsic reactivity of the metals accounts for the observed activity.

  6. Compensation effect and volcano curve in toluene hydrogenation catalyzed by transition metal sulfides.

    PubMed

    Guernalec, N; Geantet, C; Cseri, T; Vrinat, M; Toulhoat, H; Raybaud, P

    2010-09-28

    Within the framework of volcano curves, a kinetic study of toluene hydrogenation catalyzed by transition metal sulfides highlights the variation of the apparent kinetic parameters as a function of the ab initio sulfur-metal bond energy descriptor and sulfo-reductive reaction conditions. PMID:20424734

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

    ERIC Educational Resources Information Center

    Azad, Abdul-Majeed; Kesavan, Sathees

    2006-01-01

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

  8. Approaches for reducing the insulator-metal transition pressure in hydrogen

    NASA Technical Reports Server (NTRS)

    Carlsson, A. E.; Ashcroft, N. W.

    1983-01-01

    Two possible techniques for reducing the external pressure required to induce the insulator-metal transition in solid hydrogen are described. One uses impurities to lower the energy of the metallic phase relative to that of the insulating phase. The other utilizes a negative pressure induced in the insulating phase by electron-hole pairs, created either with laser irradiation or pulsed synchrotron sources.

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

    ERIC Educational Resources Information Center

    Azad, Abdul-Majeed; Kesavan, Sathees

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%, 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube.

  11. In situ study of the initiation of hydrogen bubbles at the aluminium metal/oxide interface

    NASA Astrophysics Data System (ADS)

    Xie, De-Gang; Wang, Zhang-Jie; Sun, Jun; Li, Ju; Ma, Evan; Shan, Zhi-Wei

    2015-09-01

    The presence of excess hydrogen at the interface between a metal substrate and a protective oxide can cause blistering and spallation of the scale. However, it remains unclear how nanoscale bubbles manage to reach the critical size in the first place. Here, we perform in situ environmental transmission electron microscopy experiments of the aluminium metal/oxide interface under hydrogen exposure. It is found that once the interface is weakened by hydrogen segregation, surface diffusion of Al atoms initiates the formation of faceted cavities on the metal side, driven by Wulff reconstruction. The morphology and growth rate of these cavities are highly sensitive to the crystallographic orientation of the aluminium substrate. Once the cavities grow to a critical size, the internal gas pressure can become great enough to blister the oxide layer. Our findings have implications for understanding hydrogen damage of interfaces.

  12. In situ study of the initiation of hydrogen bubbles at the aluminium metal/oxide interface.

    PubMed

    Xie, De-Gang; Wang, Zhang-Jie; Sun, Jun; Li, Ju; Ma, Evan; Shan, Zhi-Wei

    2015-09-01

    The presence of excess hydrogen at the interface between a metal substrate and a protective oxide can cause blistering and spallation of the scale. However, it remains unclear how nanoscale bubbles manage to reach the critical size in the first place. Here, we perform in situ environmental transmission electron microscopy experiments of the aluminium metal/oxide interface under hydrogen exposure. It is found that once the interface is weakened by hydrogen segregation, surface diffusion of Al atoms initiates the formation of faceted cavities on the metal side, driven by Wulff reconstruction. The morphology and growth rate of these cavities are highly sensitive to the crystallographic orientation of the aluminium substrate. Once the cavities grow to a critical size, the internal gas pressure can become great enough to blister the oxide layer. Our findings have implications for understanding hydrogen damage of interfaces. PMID:26121306

  13. Hot hydrogen testing of metallic turbo pump materials

    NASA Technical Reports Server (NTRS)

    Zee, Ralph; Chin, Bryan; Inamdar, Rohit

    1993-01-01

    The objectives of this investigation are to expose heat resistant alloys to hydrogen at elevated temperatures and to use various microstructural and analytical techniques to determine the chemical and rate process involved in degradation of these materials due to hydrogen environment. Inconel 718 and NASA-23 (wrought and cast) are candidate materials. The degradation of these materials in the presence of 1 to 5 atmospheric pressure of hydrogen from 450 C to 1100 C was examined. The hydrogen facility at Auburn University was used for this purpose. Control experiments were also conducted wherein the samples were exposed to vacuum so that a direct comparison of the results would separate the thermal contribution from the hydrogen effects. The samples were analyzed prior to and after exposure. A residual gas collection system was used to determine the gaseous species produced by any chemical reaction that may have occurred during the exposure. Analysis of this gas sample shows only the presence of H2 as expected. Analyses of the samples were conducted using optical microscopy, x-ray diffraction, scanning electron microscopy, and weight change. There appears to be no change in weight of the samples as a result of hydrogen exposure. In addition no visible change on the surface structure was detected. This indicates that the materials of interest do not have strong interaction with hot hydrogen. This is consistent with the microstructure results.

  14. Change in soft magnetic properties of Fe-based metallic glasses during hydrogen absorption and desorption

    SciTech Connect

    Novak, L.; Lovas, A.; Kiss, L.F.

    2005-08-15

    The stress level can be altered in soft magnetic amorphous alloys by hydrogen absorption. The resulting changes in the soft magnetic parameters are reversible or irreversible, depending on the chemical composition. Some of these effects are demonstrated in Fe-B, Fe-W-B, and Fe-V-B glassy ribbons, in which various magnetic parameters are measured mainly during hydrogen desorption. The rate of hydrogen desorption is also monitored by measuring the pressure change in a hermetically closed bomb. The observed phenomena are interpreted on the basis of induced stresses and chemical interactions between the solute metal and hydrogen.

  15. High-pressure chemistry of hydrogen in metals: in situ study of iron hydride.

    PubMed

    Badding, J V; Hemley, R J; Mao, H K

    1991-07-26

    Optical observations and x-ray diffraction measurements of the reaction between iron and hydrogen at high pressure to form iron hydride are described. The reaction is associated with a sudden pressure-induced expansion at 3.5 gigapascals of iron samples immersed in fluid hydrogen. Synchrotron x-ray diffraction measurements carried out to 62 gigapascals demonstrate that iron hydride has a double hexagonal close-packed structure, a cell volume up to 17% larger than pure iron, and a stoichiometry close to FeH. These results greatly extend the pressure range over which the technologically important iron-hydrogen phase diagram has been characterized and have implications for problems ranging from hydrogen degradation and embrittlement of ferrous metals to the presence of hydrogen in Earth's metallic core. PMID:17746396

  16. Predicting reaction equilibria for destabilized metal hydride decomposition reactions for reversible hydrogen storage

    SciTech Connect

    Alapati, S.V.; Johnson, J.K.; Sholl, D.S.

    2007-02-01

    Reversible storage of hydrogen still remains one of the biggest challenges for widespread use of hydrogen as a fuel. Light metal hydrides have high hydrogen content but are typically too thermodynamically stable. Destabilization of metal hydrides is an effective way to improve their thermodynamics. First principles calculations have proven to be effective for screening potential destabilized reactions, but these calculations have previously been limited to examining approximations for reaction enthalpies. We have used density functional theory calculations to calculate the reaction free energy and vant Hoff plots for a variety of potential destabilized metal hydride reactions. Our calculations suggest a multistage approach for efficiently screening new classes of metal hydrides prior to experimental studies.

  17. Method of producing metallized chloroplasts and use thereof in the photochemical production of hydrogen and oxygen

    DOEpatents

    Greenbaum, Elias (Oak Ridge, TN)

    1987-01-01

    The invention is primarily a metallized chloroplast composition for use in a photosynthetic reaction. A catalytic metal is precipitated on a chloroplast membrane at the location where a catalyzed reduction reaction occurs. This metallized chloroplast is stabilized by depositing it on a support medium such as fiber so that it can be easily handled. A possible application of this invention is the splitting of water to form hydrogen and oxygen that can be used as a renewable energy source.

  18. Metal chelator combined with permeability enhancer ameliorates oxidative stress-associated neurodegeneration in rat eyes with elevated intraocular pressure.

    PubMed

    Liu, P; Zhang, M; Shoeb, M; Hogan, D; Tang, Luosheng; Syed, M F; Wang, C Z; Campbell, G A; Ansari, N H

    2014-04-01

    Because as many as half of glaucoma patients on intraocular pressure (IOP)-lowering therapy continue to experience optic nerve toxicity, it is imperative to find other effective therapies. Iron and calcium ions play key roles in oxidative stress, a hallmark of glaucoma. Therefore, we tested metal chelation by means of ethylenediaminetetraacetic acid (EDTA) combined with the permeability enhancer methylsulfonylmethane (MSM) applied topically on the eye to determine if this noninvasive treatment is neuroprotective in rat optic nerve and retinal ganglion cells exposed to oxidative stress induced by elevated IOP. Hyaluronic acid (HA) was injected into the anterior chamber of the rat eye to elevate the IOP. EDTA-MSM was applied topically to the eye for 3 months. Eyeballs and optic nerves were processed for histological assessment of cytoarchitecture. Protein-lipid aldehyde adducts and cyclooxygenase-2 (COX-2) were detected immunohistochemically. HA administration increased IOP and associated oxidative stress and inflammation. Elevated IOP was not affected by EDTA-MSM treatment. However, oxidative damage and inflammation were ameliorated as reflected by a decrease in formation of protein-lipid aldehyde adducts and COX-2 expression, respectively. Furthermore, EDTA-MSM treatment increased retinal ganglion cell survival and decreased demyelination of optic nerve compared with untreated eyes. Chelation treatment with EDTA-MSM ameliorates sequelae of IOP-induced toxicity without affecting IOP. Because most current therapies aim at reducing IOP and damage occurs even in the absence of elevated IOP, EDTA-MSM has the potential to work in conjunction with pressure-reducing therapies to alleviate damage to the optic nerve and retinal ganglion cells. PMID:24509160

  19. Metal chelator combined with permeability enhancer ameliorates oxidative stress-associated neurodegeneration in rat eyes with elevated intraocular pressure

    PubMed Central

    Liu, P.; Zhang, M.; Shoeb, M.; Hogan, D.; Tang, Luosheng; Syed, M. F.; Wang, C. Z.; Campbell, G.A.; Ansari, N.H.

    2014-01-01

    Since as many as half of glaucoma patients on intraocular pressure (IOP)-lowering therapy continue to experience optic nerve toxicity, it is imperative to find other effective therapies. Iron and calcium ions play key roles in oxidative stress, a hallmark of glaucoma. Therefore, we tested metal chelation by means of ethylenediaminetetraacetic acid (EDTA) combined with the permeability enhancer methyl sulfonyl methane (MSM) applied topically on the eye to determine if this non-invasive treatment is neuroprotective in rat optic nerve and retinal ganglion cells exposed to oxidative stress induced by elevated IOP. Hyaluronic acid (HA) was injected in the anterior chamber of the rat eye to elevate the IOP. EDTA-MSM was applied topically to the eye for 3 months. Eyeballs and optic nerves were processed for histological assessment of cytoarchitecture. Protein-lipid aldehyde adducts, and cyclooxygnease-2 (COX-2) were detected immunohistochemically. HA administration increased IOP and associated oxidative stress and inflammation. Elevated IOP was not affected by EDTA-MSM treatment. However oxidative damage and inflammation were ameliorated as reflected by decrease in formation of protein-lipid aldehyde adducts and COX-2 expression, respectively. Furthermore, EDTA-MSM treatment increased retinal ganglion cell survival and decreased demyelinization of optic nerve compared with untreated eyes. Chelation treatment with EDTA-MSM ameliorates sequelae of IOP-induced toxicity without affecting IOP. Since most current therapies aim at reducing IOP and damage occurs even in the absence of elevated IOP, EDTA-MSM has the potential to work in conjunction with pressure-reducing therapies to alleviate damage to the optic nerve and retinal ganglion cells. PMID:24509160

  20. Molten metal reactor and method of forming hydrogen, carbon monoxide and carbon dioxide using the molten alkaline metal reactor

    DOEpatents

    Bingham, Dennis N.; Klingler, Kerry M.; Turner, Terry D.; Wilding, Bruce M.

    2012-11-13

    A molten metal reactor for converting a carbon material and steam into a gas comprising hydrogen, carbon monoxide, and carbon dioxide is disclosed. The reactor includes an interior crucible having a portion contained within an exterior crucible. The interior crucible includes an inlet and an outlet; the outlet leads to the exterior crucible and may comprise a diffuser. The exterior crucible may contain a molten alkaline metal compound. Contained between the exterior crucible and the interior crucible is at least one baffle.

  1. Method of CO and/or CO.sub.2 hydrogenation using doped mixed-metal oxides

    SciTech Connect

    Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.; Abdelsayed, Victor; Smith, Mark W.; Spivey, James J.

    2015-10-06

    A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a perovskite, a pyrochlore, a fluorite, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises an alcohol, an olefin, an aldehyde, a ketone, an ester, an oxo-product, or mixtures thereof.

  2. Small satellite nickel-hydrogen and nickel-metal hydride power applications

    NASA Astrophysics Data System (ADS)

    Cook, William Dean; Coates, Dwaine

    1993-01-01

    Nickel and silver-metal hydride batteries are being developed for aerospace applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems. Nickel-metal hydride batteries have twice the gravimetric energy density of nickel-cadmium and twice the volumetric energy density of nickel-hydrogen. Silver-metal hydride batteries have the potential of three times the energy density of nickel-metal hydride and exhibit superior charge retention characteristics. Aerospace metal hydride batteries are hermetically sealed, operate at low pressure and are prismatic in geometry. They exhibit excellent overcharge and overdischarge capability. Preliminary calorimetry data indicates superior thermal performance as compared to nickel-cadmium and nickel-hydrogen batteries. Some initial AC impedance spectroscopy work has been completed on both metal-hydrogen and metal-hydride battery systems. The objective of current programs is to develop high energy density, long cycle life metal-hydride batteries for the aerospace market and to establish a testing database to support future applications.

  3. Use of plasma arc welding process to combat hydrogen metallic disbonding of austenitic stainless steel claddings

    SciTech Connect

    Alexandrov, O.A. ); Steklov, O.I.; Alexeev, A.V. )

    1993-11-01

    A separation type crack, metallic disbonding, occurred between austenitic stainless steel weld metal cladding and 2 1/4Cr-1Mo base metal in the hydrodesulfurizing reactor of an oil refining plant. For stainless steel cladding, the submerged arc welding (SAW) process with a strip electrode is usually applied, but the authors experimented with the plasma arc welding (PAW) process with hot wire electrode for the cladding. The metallic disbonding is considered to be attributed to hydrogen accumulation at the transition zone and has been generally studied on a laboratory scale using an autoclave. The authors used a electrolytic hydrogen charging technique for the sake of experimental simplicity and made a comparison with the results for gaseous hydrogen charging. The main conclusions obtained were follows: The PAW stainless steel weld metal cladding is more resistant to metallic disbonding with the PAW process is explained by the desirable microstructure and properties of the first layer of weld metal at the transition zone. Electrolytic hydrogen charging pretty well reproduces the results of autoclave gas phase charging.

  4. Post-synthetic Ti Exchanged UiO-66 Metal-Organic Frameworks that Deliver Exceptional Gas Permeability in Mixed Matrix Membranes

    PubMed Central

    Smith, Stefan J. D.; Ladewig, Bradley P.; Hill, Anita J.; Lau, Cher Hon; Hill, Matthew R.

    2015-01-01

    Gas separation membranes are one of the lowest energy technologies available for the separation of carbon dioxide from flue gas. Key to handling the immense scale of this separation is maximised membrane permeability at sufficient selectivity for CO2 over N2. For the first time it is revealed that metals can be post-synthetically exchanged in MOFs to drastically enhance gas transport performance in membranes. Ti-exchanged UiO-66 MOFs have been found to triple the gas permeability without a loss in selectivity due to several effects that include increased affinity for CO2 and stronger interactions between the polymer matrix and the Ti-MOFs. As a result, it is also shown that MOFs optimized in previous works for batch-wise adsorption applications can be applied to membranes, which have lower demands on material quantities. These membranes exhibit exceptional CO2 permeability enhancement of as much as 153% when compared to the non-exchanged UiO-66 mixed-matrix controls, which places them well above the Robeson upper bound at just a 5 wt.% loading. The fact that maximum permeability enhancement occurs at such low loadings, significantly less than the optimum for other MMMs, is a major advantage in large-scale application due to the more attainable quantities of MOF needed. PMID:25592747

  5. Hydrogen production using metal nanoparticle modified silicon thin film photoelectrode

    NASA Astrophysics Data System (ADS)

    Yae, Shinji; Onaka, Ayumi; Abe, Makoto; Fukumuro, Naoki; Ogawa, Shunsuke; Yoshida, Norimitsu; Nonomura, Shuichi; Nakato, Yoshihiro; Matsuda, Hitoshi

    2007-09-01

    Hydrogen production using water splitting by photoelectrochemical solar cells equipped with a TiO II photoelectrode has been attracting much attention. However, TiO II encounters serious difficulty in achieving hydrogen evolution. One solution to this difficulty is using a hydrogen-producing semiconductor, such as silicon, and an oxidation reaction other than oxygen evolution, such as oxidation of iodide ions into iodine (triiodide ion). In this study, microcrystalline silicon (?c-Si:H) thin films are used as photoelectrodes in the photodecomposition of HI for low-cost and efficient production of solar hydrogen. An n-?c-3C-SiC:H and an i-?c-Si:H layer are deposited on glassy carbon substrates using the hot-wire cat-CVD method. The ?c-Si:H electrodes are modified with platinum nanoparticles through electroless displacement deposition. The platinum nanoparticles improve the electrode's stability and catalytic activity. The electrodes produce hydrogen gas and iodine via photoelectrochemical decomposition of HI with no external bias under simulated solar illumination. We also attempt solar water splitting using a multi-photon system equipped with the ?c-Si:H thin film and TiO II photoelectrodes in series.

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

    NASA Technical Reports Server (NTRS)

    Lee, Jonathan A.

    2010-01-01

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

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

    PubMed

    Schth, F; Bogdanovi?, 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). PMID:15489969

  8. Transition of single-walled carbon nanotubes from metallic to semiconducting in field-effect transistors by hydrogen plasma treatment.

    PubMed

    Zheng, Gang; Li, Qunqing; Jiang, Kaili; Zhang, Xiaobo; Chen, Jia; Ren, Zheng; Fan, Shoushan

    2007-06-01

    We report hydrogen plasma treatment results on converting the metallic single-walled carbon nanotubes to semiconducting single-walled carbon nanotubes. We found that the as-grown single-walled carbon nanotubes (SWNTs) can be sorted as three groups which behave as metallic, as-metallic, and semiconducting SWNTs. These three groups have different changes under hydrogen plasma treatment and successive annealing process. The SWNTs can be easily hydrogenated in the hydrogen plasma environment and the as-metallic SWNTs can be transformed to semiconducting SWNTs. The successive annealing process can break the C-H bond, so the conversion is reversible. PMID:17508771

  9. Vanadium diaphragm electrode serves as hydrogen diffuser in lithium hydride cell

    NASA Technical Reports Server (NTRS)

    Crouthamel, C. E.; Heinrich, R. R.; Johnson, C. E.

    1967-01-01

    Lithium hydride cell uses vanadium diaphragm electrode as a hydrogen diffuser. Vanadium is high in hydrogen gas solubility and permeability, is least sensitive to adverse surface effects, maintains good mechanical strength in hydrogen atmospheres, and appears to be compatible with all alkali-halide electrolytes and lithium metals.

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

    NASA Astrophysics Data System (ADS)

    Tanuwijaya, V. V.; Hidayat, N. N.; Agusta, M. K.; Dipojono, H. K.

    2015-09-01

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO3 sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  11. Nickel-hydrogen. [metal hydrides, electrochemical corrosion, and structural design

    NASA Technical Reports Server (NTRS)

    Mchenry, E. J.

    1977-01-01

    Because of the disintegration of LaNi5 as the lattice expands on absorbing hydrogen, a nickel hydrogen cell similar to a nickel cadmium cell was designed. The positive electrode is wrapped in a microporous separator and the leads are insulated. A negative conducting grid is inserted and welded to the top of the can into an open ended container which is then turned upside down and filled so that LiNa5 powder occupies all the space not used by the rest of the components. The bottom of the can is then welded on. A fill tube is located either on the bottom or on the top of the can. When welded shut, the cell is put into a pressure bomb and the lanthanum nickel is activated at about 1,000 pounds of hydrogen. Electrolytes are added to the cell as well as whatever amount of hydrogen precharge desired, and the cell is sealed. Advantages and disadvantages of the cell are discussed.

  12. Sonogenerated metal-hydrogen sponges for reactive hard templating.

    PubMed

    Baidukova, Olga; Möhwald, Helmuth; Mazheika, Aliaksei S; Sviridov, Dmitry V; Palamarciuc, Tatiana; Weber, Birgit; Cherepanov, Pavel V; Andreeva, Daria V; Skorb, Ekaterina V

    2015-05-01

    We present sonogenerated magnesium-hydrogen sponges for effective reactive hard templating. Formation of differently organized nanomaterials is possible by variation of sonochemical parameters and solution composition: Fe2O3 nanorods or composite dendritic Fe2O3/Fe3O4 nanostructures. PMID:25703146

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    SciTech Connect

    Zhou, Hongcai J

    2015-08-12

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

  15. Dynamic high pressure: Why it makes metallic fluid hydrogen

    NASA Astrophysics Data System (ADS)

    Nellis, W. J.

    2015-09-01

    Metallic fluid H has been made by dynamic compression decades after Wigner and Huntington (WH) predicted its existence in 1935. The density at which it was made is within a few percent of the density predicted by WH. Metallic fluid H was achieved by multiple-shock compression of liquid H2, which is quasi-isentropic and thermally equilibrated. That is, the compressions were isentropic but for enough temperature and entropy to drive the crossover to completion from H2 to H at 9-fold compression. The metallic fluid is highly degenerate: T/TF?0.014. The basic ideas of dynamic compression, also known as supersonic, adiabatic, nonlinear hydrodynamics, were developed in the last half of the Nineteenth Century in European universities. Today dynamic compression is generally unfamiliar to the scientific community, which impedes general understanding as to why fluid H becomes metallic at a pressure observable in a laboratory. The purposes of this paper are to (i) present a brief review of dynamic compression and its affects on materials, (ii) review considerations that led to the sample holder designed specifically to make metallic fluid H, and (iii) present a brief inter-comparison of dynamic and static methods to achieve high pressure relative to their prospects for making metallic H.

  16. Two-dimensional metal-organic surfaces for efficient hydrogen evolution from water.

    PubMed

    Clough, Andrew J; Yoo, Joseph W; Mecklenburg, Matthew H; Marinescu, Smaranda C

    2015-01-14

    Hydrogen production through the reduction of water has emerged as an important strategy for the storage of renewable energy in chemical bonds. One attractive scenario for the construction of efficient devices for electrochemical splitting of water requires the attachment of stable and active hydrogen evolving catalysts to electrode surfaces, which remains a significant challenge. We demonstrate here the successful integration of cobalt dithiolene catalysts into a metal-organic surface to generate very active electrocatalytic cathode materials for hydrogen generation from water. These surfaces display high catalyst loadings and remarkable stability even under very acidic aqueous solutions. PMID:25525864

  17. Catalytic Metal Free Production of Large Cage Structure Carbon Particles: A Candidate for Hydrogen Storage

    NASA Technical Reports Server (NTRS)

    Kimura, Yuki; Nuth, Joseph A., III; Ferguson, Frank T.

    2005-01-01

    We will demonstrate that carbon particles consisting of large cages can be produced without catalytic metal. The carbon particles were produced in CO gas as well as by introduction of 5% methane gas into the CO gas. The gas-produced carbon particles were able to absorb approximately 16.2 wt% of hydrogen. This value is 2.5 times higher than the 6.5 wt% goal for the vehicular hydrogen storage proposed by the Department of Energy in the USA. Therefore, we believe that this carbon particle is an excellent candidate for hydrogen storage for fuel cells.

  18. Metal-organic frameworks for the storage and delivery of biologically active hydrogen sulfide

    SciTech Connect

    Allan, Phoebe K; Wheatley, Paul S; Aldous, David; Mohideen, M Infas; Tang, Chiu; Hriljac, Joseph A; Megson, Ian L; Chapman, Karena W; De Weireld, Guy; Vaesen, Sebastian; Morris, Russell E

    2012-04-02

    Hydrogen sulfide is an extremely toxic gas that is also of great interest for biological applications when delivered in the correct amount and at the desired rate. Here we show that the highly porous metal-organic frameworks with the CPO-27 structure can bind the hydrogen sulfide relatively strongly, allowing the storage of the gas for at least several months. Delivered gas is biologically active in preliminary vasodilation studies of porcine arteries, and the structure of the hydrogen sulfide molecules inside the framework has been elucidated using a combination of powder X-ray diffraction and pair distribution function analysis.

  19. Metal-organic frameworks for the storage and delivery of biologically active hydrogen sulfide.

    PubMed

    Allan, Phoebe K; Wheatley, Paul S; Aldous, David; Mohideen, M Infas; Tang, Chiu; Hriljac, Joseph A; Megson, Ian L; Chapman, Karena W; De Weireld, Guy; Vaesen, Sebastian; Morris, Russell E

    2012-04-14

    Hydrogen sulfide is an extremely toxic gas that is also of great interest for biological applications when delivered in the correct amount and at the desired rate. Here we show that the highly porous metal-organic frameworks with the CPO-27 structure can bind the hydrogen sulfide relatively strongly, allowing the storage of the gas for at least several months. Delivered gas is biologically active in preliminary vasodilation studies of porcine arteries, and the structure of the hydrogen sulfide molecules inside the framework has been elucidated using a combination of powder X-ray diffraction and pair distribution function analysis. PMID:22378060

  20. The storage of hydrogen in the form of metal hydrides: An application to thermal engines

    NASA Technical Reports Server (NTRS)

    Gales, C.; Perroud, P.

    1981-01-01

    The possibility of using LaNi56, FeTiH2, or MgH2 as metal hydride storage sytems for hydrogen fueled automobile engines is discussed. Magnesium copper and magnesium nickel hydrides studies indicate that they provide more stable storage systems than pure magnesium hydrides. Several test engines employing hydrogen fuel have been developed: a single cylinder motor originally designed for use with air gasoline mixture; a four-cylinder engine modified to run on an air hydrogen mixture; and a gas turbine.

  1. Hydrogen-induced cracking along the fusion boundary of dissimilar metal welds

    SciTech Connect

    Rowe, M.D.; Nelson, T.W.; Lippold, J.C.

    1999-02-01

    Presented here are the results from a series of experiments in which dissimilar metals welds were made using the gas tungsten arc welding process with pure argon or argon-6% hydrogen shielding gas. The objective was to determine if cracking near the fusion boundary of dissimilar metal welds could be caused by hydrogen absorbed during welding and to characterize the microstructures in which cracking occurred. Welds consisted of ER308 and ER309LSi austenitic stainless steel and ERNiCr-3-nickel-based filler metals deposited on A36 steel base metal. Cracking was observed in welds made with all three filler metals. A ferrofluid color metallography technique revealed that cracking was confined to regions in the weld metal containing martensite. Microhardness indentations indicated that martensitic regions in which cracking occurred had hardness values from 400 to 550 HV. Cracks did not extend into bulk weld metal with hardness less than 350 HV. Martensite formed near the fusion boundary in all three filler metals due to regions of locally increased base metal dilution.

  2. High Flux Metallic Membranes for Hydrogen Recovery and Membrane Reactors

    SciTech Connect

    Buxbaum, Robert

    2010-06-30

    We made and tested over 250 new alloys for use as lower cost, higher flux hydrogen extraction membrane materials. Most of these were intermetallic, or contained significant intermetallic content, particularly based on B2 alloy compositions with at least one refractory component; B2 intermetallics resemble BCC alloys, in structure, but the atoms have relatively fixed positions, with one atom at the corners of the cube, the other at the centers. The target materals we were looking for would contain little or no expensive elements, no strongly toxic or radioactive elements, would have high flux to hydrogen, while being fabricable, brazable, and relatively immune to hydrogen embrittlement and corrosion in operation. The best combination of properties of the membrane materials we developed was, in my opinion, a Pd-coated membrane consisting of V -9 atomic % Pd. This material was relatively cheap, had 5 times the flux of Pd under the same pressure differential, was reasonably easy to fabricate and braze, and not bad in terms of embrittlement. Based on all these factors we project, about 1/3 the cost of Pd, on an area basis for a membrane designed to last 20 years, or 1/15 the cost on a flux basis. Alternatives to this membrane replaced significant fractions of the Pd with Ni and or Co. The cost for these membranes was lower, but so was the flux. We produced successful brazed products from the membrane materials, and made them into flat sheets. We tested, unsuccessfully, several means of fabricating thematerials into tubes, and eventually built a membrane reactor using a new, flat-plate design: a disc and doughnut arrangement, a design that seems well- suited to clean hydrogen production from coal. The membranes and reactor were tested successfully at Western Research. A larger equipment company (Chart Industries) produced similar results using a different flat-plate reactor design. Cost projections of the membrane are shown to be attractive.

  3. Hydrogen-on-demand using metallic alloy nanoparticles in water.

    PubMed

    Shimamura, Kohei; Shimojo, Fuyuki; Kalia, Rajiv K; Nakano, Aiichiro; Nomura, Ken-Ichi; Vashishta, Priya

    2014-07-01

    Hydrogen production from water using Al particles could provide a renewable energy cycle. However, its practical application is hampered by the low reaction rate and poor yield. Here, large quantum molecular dynamics simulations involving up to 16,611 atoms show that orders-of-magnitude faster reactions with higher yields can be achieved by alloying Al particles with Li. A key nanostructural design is identified as the abundance of neighboring Lewis acid-base pairs, where water-dissociation and hydrogen-production require very small activation energies. These reactions are facilitated by charge pathways across Al atoms that collectively act as a "superanion" and a surprising autocatalytic behavior of bridging Li-O-Al products. Furthermore, dissolution of Li atoms into water produces a corrosive basic solution that inhibits the formation of a reaction-stopping oxide layer on the particle surface, thereby increasing the yield. These atomistic mechanisms not only explain recent experimental findings but also predict the scalability of this hydrogen-on-demand technology at industrial scales. PMID:24960149

  4. Systems and methods for selective hydrogen transport and measurement

    DOEpatents

    Glatzmaier, Gregory C

    2013-10-29

    Systems and methods for selectively removing hydrogen gas from a hydrogen-containing fluid volume are disclosed. An exemplary system includes a proton exchange membrane (PEM) selectively permeable to hydrogen by exclusively conducting hydrogen ions. The system also includes metal deposited as layers onto opposite sides or faces of the PEM to form a membrane-electrode assembly (MEA), each layer functioning as an electrode so that the MEA functions as an electrochemical cell in which the ionic conductors are hydrogen ions, and the MEA functioning as a hydrogen selective membrane (HSM) when located at the boundary between a hydrogen-containing fluid volume and a second fluid.

  5. Pressure effects on hydrogen atoms near the metal plane in the HCP phase of rare-earth metal trihydrides

    NASA Astrophysics Data System (ADS)

    Tunghathaithip, N.; Pakornchote, T.; Phaisangittisakul, N.; Bovornratanaraks, T.; Pinsook, U.

    2016-04-01

    Rare-earth metal trihydrides, REH3 (RE=Sc, Y, La), in the hcp phase were investigated under high pressure by the ab initio method. We concentrated on the behavior of hydrogen atoms which is affected by pressure. Two-thirds of the hydrogen atoms near the metal plane (Hm) were found to displace away from the metal plane as pressure increases. The trajectory of these squeezed hydrogen atoms is from a site near the metal plane, and moves past the plane of the tetragonal sites, and heads toward the nearest octahedral site. However, the rate of displacement depends on the local environment. LaH3 exhibits the least impediment on the Hm displacement while YH3 and ScH3 exhibit stronger impediment. Furthermore, our calculated Raman and IR active modes are in general agreement with the experimental data. The displacement of Hm can be used to explain the behavior of the Ov peak in Raman spectra, where it exists at low pressure and disappears at higher pressure in YH3 and ScH3.

  6. Enantioselective hydrogenation. IV. Hydrogen isotope exchange in 10,11-dihydrocinchonidine and in quinoline catalyzed by platinum group metals

    SciTech Connect

    Bond, G.; Wells, P.B.

    1994-12-01

    Hydrogen isotope (H/D) exchange in the alkaloid 10,11-dihydrocinchonidine has been studied over 6.4% Pt/silica (EUROPT-1), 5% Ru/alumina, 5% Rh/alumina, and 5% Pd/alumina at 293 K using C{sub 2}H{sub 5}OD and D{sub 2} as solvent and deuterium source. Exchange was accompanied by hydrogenation. Over Pt, fast exchange occurred in the hydroxyl group followed by multiple exchange in which alkaloid molecules containing, 2, 3, 4 and 5 deuterium atoms were formed simultaneously. Mass spectrometry and {sup 1}H NMR showed that this multiple exchange occurred in the quinoline ring system and at C{sub 9}, but not in the quinuclidine ring system. The pattern of exchange in Ru was similar. Over Rh extensive hydrogenolysis of the quinuclidine ring system occurred, and over Pd the quinoline ring system was rapidly hydrogenated. Quinoline exchange and hydrogenation were also studied at 293 K; relatively rapid exchange occurred over Pt, Ru, and Rh, particularly at the 2- and 8-positions, whereas hydrogenation without significant exchange occurred over Pd. 10,11-Dihydrocinchonidine is adsorbed on Pt and Ru via the quinoline ring system and the multiple nature of the exchange indicates that the quinoline moiety is adsorbed approximately parallel to the metal surface by multicenter {pi}-bonding. An additional interaction of the alkaloid molecule with the surface occurs at carbon atom C{sub 9}, which may interpret the slower exchange in the alkaloid by comparison with that in quinoline. This study supports and enhances the model proposed to interpret the origin of enantioselectivity in pyruvate hydrogenation over Pt and Ir modified by cinchona alkaloids. The similarities of exchange over Pt and Ru suggest that enantioselective catalysis should be achievable over Ru. 28 refs., 2 figs., 2 tabs.

  7. Gas tungsten arc and low hydrogen shielded metal arc welding of carbon steel. Welding procedure specification

    SciTech Connect

    Wodtke, C.H.; Frizzell, D.R.; Plunkett, W.A.

    1985-08-01

    Procedure WPS-128-ASME-1 is qualified under Section IX of the ASME Boiler and Pressure Vessel Code for gas tungsten arc and low hydrogen shielded metal arc welding of carbon steels (P-1-1), in thickness range 0.25 to 2 inch; filler metals are ER70S-3 (F-6, A-1) (GTAW) and E7018 (F-4, A-1); shielding gas is argon (GTAW).

  8. Chiral-at-metal iridium complex for efficient enantioselective transfer hydrogenation of ketones.

    PubMed

    Tian, Cheng; Gong, Lei; Meggers, Eric

    2016-03-01

    A bis-cyclometalated iridium(iii) complex with metal-centered chirality catalyzes the enantioselective transfer hydrogenation of ketones with high enantioselectivities at low catalyst loadings down to 0.002 mol%. Importantly, the rate of catalysis and enantioselectivity are markedly improved in the presence of a pyrazole co-ligand. The reaction is proposed to proceed via an iridium-hydride intermediate exploiting metal-ligand cooperativity (bifunctional catalysis). PMID:26911401

  9. Hierarchical Transition-Metal Dichalcogenide Nanosheets for Enhanced Electrocatalytic Hydrogen Evolution.

    PubMed

    Zhang, Jian; Liu, Shaohua; Liang, Haiwei; Dong, Renhao; Feng, Xinliang

    2015-12-01

    Hierarchical transition-metal dichalcogenide nanosheets are constructed through a versatile strategy, where the thermal polymerization of melamine and subsequent decomposition of carbon nitride successively guide the horizontal and vertical growths of transition-metal chalcogenides. Abundant edges and high surface areas endow the hierarchical MoS2 and WS2 nanosheets with excellent electrocatalytic performance for hydrogen evolution, including low onset potentials and high current densities. PMID:26485666

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

    SciTech Connect

    Koopman, D

    2008-06-25

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

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

    SciTech Connect

    Bannochie, C

    2005-09-01

    The Defense Waste Processing Facility, DWPF, has requested that the Savannah River National Laboratory, SRNL, investigate the factors that contribute to hydrogen generation to determine if current conservatism in setting the DWPF processing window can be reduced. A phased program has been undertaken to increase understanding of the factors that influence hydrogen generation in the DWPF Chemical Process Cell, CPC. The hydrogen generation in the CPC is primarily due to noble metal catalyzed decomposition of formic acid with a minor contribution from radiolytic processes. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Two sludge simulants were obtained, one with co-precipitated noble metals and one without noble metals. Co-precipitated noble metals were expected to better match real waste behavior than using trimmed noble metals during CPC simulations. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The two original and two heat-treated sludge simulants were then used as feeds to Sludge Receipt and Adjustment Tank, SRAT, process simulations. Testing was done at relatively high acid stoichiometries, {approx}175%, and without mercury in order to ensure significant hydrogen generation. Hydrogen generation rates were monitored during processing to assess the impact of the form of noble metals. The following observations were made on the data: (1) Co-precipitated noble metal simulant processed similarly to trimmed noble metal simulant in most respects, such as nitrite to nitrate conversion, formate destruction, and pH, but differently with respect to hydrogen generation: (A) The peak hydrogen generation rate occurred three to five hours later for the regular and heat-treated co-precipitated noble metal slurries than for the slurries with trimmed noble metals. (B) The peak hydrogen generation rate was lower during processing of the co-precipitated noble metal simulant relative to the trimmed noble metal simulant data. (C) Trimmed noble metals appeared to be conservative relative to co-precipitated noble metals under the conditions of these tests as long as the peak hydrogen generation rate occurred early in the SRAT boiling period. (2) If the peak hydrogen generation rate with trimmed noble metals is near or above the DWPF limit, and if the peak occurs late in the SRAT cycle, then a potential SME cycle hydrogen generation rate issue could be anticipated when using co-precipitated noble metals, since the peak is expected to be delayed relative to trimmed noble metals. (3) The peak hydrogen generation rate increased from about 1.3 to about 3.7 lbs H{sub 2}/hr on the range of 170-190% stoichiometry, or about 0.1 lbs. H{sub 2}/hr per % change in the stoichiometric factor at DWPF scale. (4) The peak generation rate was slightly higher during processing of the heat-treated coprecipitated noble metal simulant relative to the trimmed noble metal heat-treated simulant, but this probably due to somewhat more excess acid being added to the co-precipitated noble metal test than intended. (5) The variations in the peak hydrogen generation rate appeared to track the quantity of dissolved rhodium in the SRAT product. (6) A noble metal apparently activated and then de-activated during the final hour of formic acid addition. The associated peak generation rate was <3% of the maximum rate seen in each test. Palladium may have been responsible based on literature data. (7) Planned comparisons between heat-treated and un-heat-treated simulants were complicated by the significantly altered base equivalents following heat-treatment. This necessitated making small adjustments to the stoichiometric acid factor to attempt to match the excess acid contents

  12. Dynamic high pressure: why it makes metallic fluid hydrogen

    NASA Astrophysics Data System (ADS)

    Nellis, William

    2015-06-01

    Metallic fluid H (MFH) was made by dynamic compression decades after Wigner and Huntington (WH) predicted it in 1935. The density of MFH is within a few percent of the density predicted by WH. MFH was made by multiple-shock compression of liquid H2, which process is quasi-isentropic and thermally equilibrated. The compressions were isentropic but produced enough dissipation as temperature T and entropy S to drive the crossover from insulating H2 to metallic H at 9-fold compressed atomic H density. T and S were tuned by temporally shaping the applied pressure pulse such that H2 dissociated to H at sufficiently high density to make a highly degenerate metal. The basic ideas of dynamic compression, also known as supersonic, adiabatic, nonlinear hydrodynamics, were developed in the last half of the Nineteenth Century. Our purposes are to (i) present a brief review of dynamic compression and its affects on materials, (ii) review considerations that led to the sample holder designed specifically to make MFH, and (iii) present a inter-comparison of dynamic and static methods relative to their prospects for making metallic H.

  13. TREATMENT OF METALS IN GROUND WATER USING AN ORGANIC-BASED SULFATE-REDUCING PERMEABLE REACTIVE BARRIER

    EPA Science Inventory

    A pilot permeable reactive barrier (PRB) consisting of a mixture of leaf compost, zero-valent iron (ZVI) filings, limestone and pea gravel was evaluated at a former phosphate fertilizer manufacturing facility in Charleston, S.C. The PRB is designed to treat arsenic and heavy met...

  14. The hydrogenation of metals upon interaction with water

    NASA Technical Reports Server (NTRS)

    Andreyev, L. A.; Gelman, B. G.; Zhukhovitskiy, A. A.; Polosina, Y. Y.

    1979-01-01

    Hydrogen evolution at 600 deg and 5 x 10 to the 7th power - 10 to the 6th power torr from AVOOO Al samples, which were pickled in 10 percent NaOH, is discussed. An H evolution kinetic equation is derived for samples of equal vol. and different surfaces (5 and 20 sq cm). The values of the H evolution coefficient K indicated an agreement with considered H diffusion mechanism through an oxide layer. The activation energy for the H evolution process, obtained from the K-temp. relation, was 13,000 2000 cal/g-atom.

  15. Hydrogen permeation in metals near room temperature by a tritium tracer technique

    NASA Astrophysics Data System (ADS)

    Ikeda, Takahiro; Otsuka, Teppei; Tanabe, Tetsuo

    2011-10-01

    In a fusion reactor, tritium retention and permeation in structure materials are very important safety concerns. Most data for diffusion and permeation of hydrogen in metals so far available have been limited for rather higher temperatures and, in particular, no data are available for high-Z metals near room temperature (RT). We have tried to observe gaseous hydrogen permeation through metals near RT applying a tritium tracer technique, which is a very powerful tool to detect quite small amount of hydrogen (tritium) by a liquid scintillation counting (LSC) method. After confirming the reliability of the method for the determination of diffusion and permeation coefficients in pure Ni, it was applied to hydrogen permeation in W near RT, and diffusion and permeation coefficients of hydrogen in W were determined, D=(3.420.68)10-9exp((-37.81.2)(kJ/mol)/RT),m s, and ?=(1.210.24)10-5exp((-57.80.9)(kJ/mol)/RT),mol m s Pa.

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

    NASA Astrophysics Data System (ADS)

    Bates, Michael

    Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).

  17. Trends in Selective Hydrogen Peroxide Production on Transition Metal Surfaces from First Principles

    SciTech Connect

    Rankin, Rees B.; Greeley, Jeffrey P.

    2012-10-19

    We present a comprehensive, Density Functional Theory-based analysis of the direct synthesis of hydrogen peroxide, H2O2, on twelve transition metal surfaces. We determine the full thermodynamics and selected kinetics of the reaction network on these metals, and we analyze these energetics with simple, microkinetically motivated rate theories to assess the activity and selectivity of hydrogen peroxide production on the surfaces of interest. By further exploiting Brønsted-Evans-Polanyi relationships and scaling relationships between the binding energies of different adsorbates, we express the results in the form of a two dimensional contour volcano plot, with the activity and selectivity being determined as functions of two independent descriptors, the atomic hydrogen and oxygen adsorption free energies. We identify both a region of maximum predicted catalytic activity, which is near Pt and Pd in descriptor space, and a region of selective hydrogen peroxide production, which includes Au. The optimal catalysts represent a compromise between activity and selectivity and are predicted to fall approximately between Au and Pd in descriptor space, providing a compact explanation for the experimentally known performance of Au-Pd alloys for hydrogen peroxide synthesis, and suggesting a target for future computational screening efforts to identify improved direct hydrogen peroxide synthesis catalysts. Related methods of combining activity and selectivity analysis into a single volcano plot may be applicable to, and useful for, other aqueous phase heterogeneous catalytic reactions where selectivity is a key catalytic criterion.

  18. Defect structure and transport properties of Ni-SrCeO{sub 3-delta} cermet for hydrogen separation membrane.

    SciTech Connect

    Song, S.-J.; Lee, T. H.; Wachsman, E. D.; Chen, L.; Dorris, S. E.; Balachandran, U.; Energy Technology; Univ. of Florida

    2005-01-01

    Research on hydrogen separation membranes is motivated by the increasing demand for an environmentally benign, inexpensive technology for separating hydrogen from gas mixtures. Although most studies of hydrogen separation membranes have focused on proton-conducting oxides by themselves, the addition of metal to these oxides increases their hydrogen permeability and improves their mechanical stability. This study began by determining hydrogen permeation properties of SrCe0.8Yb0.2O3-delta (SCYb). The results showed that at the investigated temperatures (600-900 degrees C), the hydrogen permeation rate is limited by electron flow. To further enhance hydrogen permeability, a cermet (i.e., ceramic-metal composite) membrane was made by adding Ni to the SCYb. At 900 degrees C, with 20% H-2/balance He as a feed gas (p(H2O) = 0.03 atm), the hydrogen permeation rate was 0.105 cm(3)/min cm(2) for 0.25-mm-thick Ni/SCYb and 0.008 cm(3)/min cm(2) for SCYb (0.7-mm thick). The dependence of hydrogen permeability on temperature and hydrogen partial-pressure gradients was also determined. The proton conductivity (approximate to ambipolar conductivity) was extracted from the dependence of hydrogen permeability on hydrogen potential gradients. The results demonstrate that adding Ni to SCYb considerably increases its hydrogen permeability by increasing its electron conductivity.

  19. Phonons in quantum solids with defects. [lattice vacancies and interstitials in solid helium and metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Jacobi, N.; Zmuidzinas, J. S.

    1974-01-01

    A formalism was developed for temperature-dependent, self-consistent phonons in quantum solids with defects. Lattice vacancies and interstitials in solid helium and metallic hydrogen, as well as electronic excitations in solid helium, were treated as defects that modify properties of these systems. The information to be gained from the modified phonon spectrum is discussed.

  20. Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor

    DOEpatents

    Dhooge, Patrick M. (Corrales, NM)

    1987-10-13

    A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.

  1. Enhancing electrocatalytic hydrogen evolution by nickel salicylaldimine complexes with alkali metal cations in aqueous media.

    PubMed

    Shao, Haiyan; Muduli, Subas K; Tran, Phong D; Soo, Han Sen

    2016-02-01

    New salicylaldimine nickel complexes, comprising only earth-abundant elements, have been developed for electrocatalytic hydrogen evolution in aqueous media. The second-sphere ether functionalities on the periphery of the complexes enhance the electrocatalytic activity in the presence of alkali metal cations. The electrocatalysts demonstrate improved performances especially in the economical and sustainable seawater reaction medium. PMID:26779580

  2. Butterfly valve with metal seals controls flow of hydrogen from cryogenic through high temperatures

    NASA Technical Reports Server (NTRS)

    Johnson, L. D.

    1967-01-01

    Butterfly valve with metal seals operates over a temperature range of minus 423 degrees to plus 440 degrees F with hydrogen as a medium and in a radiation environment. Media flow is controlled by an internal butterfly disk which is rotated by an actuation shaft.

  3. Hydrogen storage materials: room-temperature wet-chemistry approach toward mixed-metal borohydrides.

    PubMed

    Jaro?, Tomasz; Or?owski, Piotr A; Wegner, Wojciech; Fija?kowski, Karol J; Leszczy?ski, Piotr J; Grochala, Wojciech

    2015-01-19

    The poor kinetics of hydrogen evolution and the irreversibility of the hydrogen discharge hamper the use of transition metal borohydrides as hydrogen storage materials, and the drawbacks of current synthetic methods obstruct the exploration of these systems. A wet-chemistry approach, which is based on solvent-mediated metathesis reactions of precursors containing bulky organic cations and weakly coordinating anions, leads to mixed-metal borohydrides that contain only a small amount of "dead mass". The applicability of this method is exemplified by Li[Zn2(BH4)5] and M[Zn(BH4)3] salts (M=Na, K), and its extension to other systems is discussed. PMID:25470241

  4. Vacancy trapping mechanism for hydrogen bubble formation in metal

    SciTech Connect

    Liu Yuelin; Zhang Ying; Zhou Hongbo; Lu Guanghong; Liu Feng; Luo, G.-N.

    2009-05-01

    We reveal the microscopic vacancy trapping mechanism for H bubble formation in W based on first-principles calculations of the energetics of H-vacancy interaction and the kinetics of H segregation. Vacancy provides an isosurface of optimal charge density that induces collective H binding on its internal surface, a prerequisite for the formation of H{sub 2} molecule and nucleation of H bubble inside the vacancy. The critical H density on the vacancy surface before the H{sub 2} formation is found to be 10{sup 19}-10{sup 20} H atoms per m{sup 2}. We believe that such mechanism is generally applicable for H bubble formation in metals and metal alloys.

  5. Phase transition into the metallic state in hypothetical (without molecules) dense atomic hydrogen

    SciTech Connect

    Khomkin, A. L. Shumikhin, A. S.

    2013-10-15

    A simple physical model of the metal-dielectric (vapor-liquid) phase transition in hypothetical (without molecules) atomic hydrogen is proposed. The reason for such a transition is the quantum collective cohesive energy occurring due to quantum electron-electron exchange similar to the cohesive energy in the liquid-metal phase of alkali metals. It is found that the critical parameters of the transition are P{sub c} ? 41000 atm, ?{sub c} ? 0.1 g/cm{sup 3}, and T{sub c} ? 9750 K.

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

    NASA Technical Reports Server (NTRS)

    Nelson, H. G.

    1972-01-01

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

  7. Crustal Permeability

    NASA Astrophysics Data System (ADS)

    Ingebritsen, S.; Gleeson, T.

    2014-12-01

    Existing data and models support a distinction between the hydrodynamics of the brittle upper crust, where topography, permeability contrasts, and magmatic heat sources dominate patterns of flow and externally derived (meteoric) fluids are common, and the ductile lower crust, dominated by devolatilization reactions and internally derived fluids. The permeability structure of the uppermost (~<1 km) crust is highly heterogeneous, and controls include primary lithology, porosity, rheology, geochemistry, and tectonic and time-temperature histories of the rocks. Systematic permeability differences among original lithologies persist to contact-metamorphic depths of 3-10 km, but are not evident at regional-metamorphic depths of 10-30+ km - presumably because, at such depths, metamorphic textures become largely independent of the original lithology. Permeability can vary in time as well as space, and its temporal evolution may be gradual or abrupt: streamflow responses to moderate to large earthquakes demonstrate that dynamic stresses can instantaneously change permeability by factors of up to 20 on a regional scale, whereas a 10-fold decrease in the permeability of a package of shale in a compacting basin may require 107years. Temporal variation is enhanced by strong chemical and thermal disequilibrium; thus lab experiments involving hydrothermal flow in crystalline rocks under pressure, temperature, and chemistry gradients often result in 10-fold permeability decreases over daily to sub-annual time scales. Recent research on enhanced geothermal reservoirs, ore-forming systems, and the hydrologic effects of earthquakes consistently shows that shear dislocation caused by tectonic forcing or fluid injection can increase near-to intermediate-field permeability by factors of 100 to 1000. Nonetheless, considering permeability as static parameter is often a reasonable assumption for low-temperature hydrogeologic investigations with time scales of days to decades.

  8. Two-Dimensional Metal Dichalcogenides and Oxides for Hydrogen Evolution: A Computational Screening Approach.

    PubMed

    Pandey, Mohnish; Vojvodic, Aleksandra; Thygesen, Kristian S; Jacobsen, Karsten W

    2015-05-01

    We explore the possibilities of hydrogen evolution by basal planes of 2D metal dichalcogenides and oxides in the 2H and 1T class of structures using the hydrogen binding energy as a computational activity descriptor. For some groups of systems like the Ti, Zr, and Hf dichalcogenides the hydrogen bonding to the 2H structure is stronger than that to the 1T structure, while for the Cr, Mo, and W dichalcogenides the behavior is opposite. This is rationalized by investigating shifts in the chalcogenide p levels comparing the two structures. We find that usually for a given material only at most one of the two phases will be active for the hydrogen evolution reaction; however, in most cases the two phases are very close in formation energy, opening up the possibility for stabilizing the active phase. The study points to many new possible 2D HER materials beyond the few that are already known. PMID:26263317

  9. Grain-boundary engineering markedly reduces susceptibility to intergranular hydrogen embrittlement in metallic materials

    SciTech Connect

    Bechtle, Sabine; Kumar, Mukul; Somerday, Brian P.; Launey, Maximilien E.; Ritchie, Robert O.

    2009-05-10

    The feasibility of using 'grain-boundary engineering' techniques to reduce the susceptibility of a metallic material to intergranular embrittlement in the presence of hydrogen is examined. Using thermomechanical processing, the fraction of 'special' grain boundaries was increased from 46% to 75% (by length) in commercially pure nickel samples. In the presence of hydrogen concentrations between 1200 and 3400 appm, the high special fraction microstructure showed almost double the tensile ductility; also, the proportion of intergranular fracture was significantly lower and the J{sub c} fracture toughness values were some 20-30% higher in comparison with the low special fraction microstructure. We attribute the reduction in the severity of hydrogen-induced intergranular embrittlement to the higher fraction of special grain boundaries, where the degree of hydrogen segregation at these boundaries is reduced.

  10. Thermomechanics of a metal hydride-based hydrogen tank

    NASA Astrophysics Data System (ADS)

    Lexcellent, Christian; Gay, Guillaume; Chapelle, David

    2015-05-01

    In this paper, a thermodynamical model of a porous media made of one or two solid phases α and β (depending on the hydrogen concentration) and one gas phase H2 is presented. As an extension of previous works performed by Gondor and Lexcellent (Int J Hydrog Energy 34(14):5716-5725, doi: 10.1016/j.ijhydene.2009.05.070, 2009), our attention is paid to the identification of the vectorial displacement and by consequence to the stress and strain states in every point of the tank. This study allows a safe design of the reservoir. In front of the complexity of the problem to solve, a synthesis and a table of unknowns, constants, and parameters will ease the reader understanding. The problem is restricted to the isotropic elastic behavior of the solid phases. A great ingredient of the investigation is the phase transformation between the two phases α and β.

  11. Permeability of porour rhyolite

    NASA Astrophysics Data System (ADS)

    Cashman, K.; Rust, A.; Wright, H.; Roberge, J.

    2003-04-01

    The development of permeability in bubble-bearing magmas determines the efficiency of volatile escape during their ascent through volcanic conduits, which, in turn, controls their explosive potential. As permeability requires bubble connectivity, relationships between permeability and porosity in silicic magmas must be controlled by the formation, growth, deformation and coalescence of their constituent bubbles. Although permeability data on porous volcanic pyroclasts are limited, the database can be greatly extended by including data for ceramic and metallic foams1. Several studies indicate that a single number does not adequately describe the permeability of a foam because inertial effects, which predominate at high flow rates, cause deviations from Darcy's law. These studies suggest that permeability is best modeled using the Forschheimer equation to determine both the Darcy permeability (k1) and the non-Darcian (k2) permeability. Importantly, at the high porosities of ceramic foams (75-95%), both k1 and k2 are strongly dependent on pore size and geometry, suggesting that measurement of these parameters provides important information on foam structure. We determined both the connected porosity (by He-pycnometry) and the permeability (k1 and k2) of rhyolitic samples having a wide range in porosity (22-85%) and vesicle textures. In general, these data support previous observations of a power law relationship between connected porosity and Darcy permeability2. In detail, variations in k1 increase at higher porosities. Similarly, k2 generally increases in both mean and standard deviation with increasing porosity. Measurements made on three mutually perpendicular cores from individual pumice clasts suggest that some of the variability can be explained by anisotropy in the vesicle structure. By comparison with ceramic foams, we suggest that the remaining variability results from differences either in average vesicle size or, more likely, in the size of apertures connecting individual vesicles. This interpretation is supported by the observation that clasts with high porosities but unusually low k1 and k2 also have high percentages of isolated pores (>10%), indicating extensive vesiculation but limited bubble coalescence; such clasts seem to be characteristic of ignimbrite deposits. 1Innocentini MDM, Salvini VR, Pandolfelli VC, Coury JC (1999) The permeability of ceramic foams. Amer Ceram Soc Bull 79:78-94. 2Klug C, Cashman KV (1996) Permeability development in vesiculating magmas - implications for fragmentation. Bull. Volcanol.58:87-100; Klug C, Cashman KV, Bacon C (2002) Structure and physical characteristics of pumice from the climactic eruption of Mt. Mazama (Crater Lake), Oregon. Bull Volcanol 64:486-501

  12. Hydrogen mimicking the properties of coinage metal atoms in Cu and Ag monohydride clusters.

    PubMed

    Vetter, Karsten; Proch, Sebastian; Gantefr, Gerd F; Behera, Swayamprabha; Jena, Puru

    2013-12-28

    A systematic study of the electronic structure and equilibrium geometries of Cun, Cun-1H, Agn, and Agn-1H; n = 2-5 clusters is carried out using photoelectron spectroscopy (PES) experiments and density functional theory based calculations. Our objective is to see if the substitution of a coinage metal atom by hydrogen would retain the electronic structure of the parent metal cluster since both systems are isoelectronic. For clusters with n ? 3, we find that the measured PES and vertical detachment energies (VDEs) (i.e. energies necessary to remove an electron from the anionic Mn(-) (M = Cu, Ag) clusters without changing their geometries) are close to those of Mn-1H(-) clusters, suggesting that substitution of a metal atom with hydrogen does not perturb the electronic structure of the parent cluster anion significantly. Calculated VDEs agree very well with experiment validating the theoretical methods used as well as the geometries of the neutral and anionic clusters. PMID:24217243

  13. 2D Transition-Metal-Dichalcogenide-Nanosheet-Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions.

    PubMed

    Lu, Qipeng; Yu, Yifu; Ma, Qinglang; Chen, Bo; Zhang, Hua

    2016-03-01

    Hydrogen (H2 ) is one of the most important clean and renewable energy sources for future energy sustainability. Nowadays, photocatalytic and electrocatalytic hydrogen evolution reactions (HERs) from water splitting are considered as two of the most efficient methods to convert sustainable energy to the clean energy carrier, H2 . Catalysts based on transition metal dichalcogenides (TMDs) are recognized as greatly promising substitutes for noble-metal-based catalysts for HER. The photocatalytic and electrocatalytic activities of TMD nanosheets for the HER can be further improved after hybridization with many kinds of nanomaterials, such as metals, oxides, sulfides, and carbon materials, through different methods including the in situ reduction method, the hot-injection method, the heating-up method, the hydro(solvo)thermal method, chemical vapor deposition (CVD), and thermal annealing. Here, recent progress in photocatalytic and electrocatalytic HERs using 2D TMD-based composites as catalysts is discussed. PMID:26676800

  14. Selective etching of metallic single-wall carbon nanotubes with hydrogen plasma.

    PubMed

    Hassanien, A; Tokumoto, M; Umek, P; Vrbanič, D; Mozetič, M; Mihailović, D; Venturini, P; Pejovnik, S

    2005-02-01

    We present Raman scattering and scanning tunnelling microscopy (STM) measurements on hydrogen plasma etched single-wall carbon nanotubes (SWNTs). Interestingly, both the STM and Raman spectroscopy show that the metallic SWNTs are dramatically altered and highly defected by the plasma treatment. In addition, structural characterizations show that metal catalysts are detached from the ends of the SWNT bundles. For semiconducting SWNTs we observe no feature of defects or etching along the nanotubes. Raman spectra in the radial breathing mode region of plasma-treated SWNT material show that most of the tubes are semiconducting. These results show that hydrogen plasma treatment favours etching of metallic nanotubes over semiconducting ones and therefore could be used to tailor the electronic properties of SWNT raw materials. PMID:21727436

  15. Investigation of the feasibility of developing low permeability polymeric films

    NASA Technical Reports Server (NTRS)

    Hoggatt, J. T.

    1971-01-01

    The feasibility of reducing the gas permeability rate of Mylar and Kapton films without drastically effecting their flexibility characteristics at cryogenic temperatures was considered. This feasibility was established using a concept of diffusion bonding two layers of metallized films together forming a film-metal-film sandwich laminate. The permeability of kapton film to gaseous helium was reduced from a nominal ten = to the minus 9 power cc-mm/sq cm sec. cm Hg to ten to the minus 13 power cc-mm/ sq cm - sec. cm Hg with some values as low as ten to the minus 15 power cc - mm/sq cm m-sec - cm Hg being obtained. Similar reductions occurred in the liquid hydrogen permeability at -252 C. In the course of the program the permeability, flexibility and bond strength of plain, metalized and diffusion bond film were determined at +25 C, -195 C and -252 C. The cryogenic flexibility of Kapton film was reduced slightly due to the metallization process but no additional loss in flexibility resulted from the diffusion bonding process.

  16. First-principles calculations of transition metal solute interactions with hydrogen in tungsten

    NASA Astrophysics Data System (ADS)

    Kong, Xiang-Shan; Wu, Xuebang; Liu, C. S.; Fang, Q. F.; Hu, Q. M.; Chen, Jun-Ling; Luo, G.-N.

    2016-02-01

    We have performed systematic first-principles calculations to predict the interaction between transition metal (TM) solutes and hydrogen in the interstitial site as well as the vacancy in tungsten. We showed that the site preference of the hydrogen atom is significantly influenced by the solute atoms, which can be traced to the charge density perturbation in the vicinity of the solute atom. The solute-H interactions are mostly attractive except for Re, which can be well understood in terms of the competition between the chemical and elastic interactions. The chemical interaction dominates the solute-H interaction for the TM solutes with a large atomic volume and small electronegativity compared to tungsten, while the elastic interaction is primarily responsible for the solute-H interaction for the TM solutes with a small atomic volume and large electronegativity relative to tungsten. The presence of a hydrogen atom near the solute atom has a negative effect on the binding of other hydrogen atoms. The large positive binding energies among the solute, vacancy and hydrogen suggest that they would easily form a defect cluster in tungsten, where the solute-vacancy and vacancy-H interaction contribute greatly while the solute-H interaction contributes a little. Our result provides a sound theoretical explanation for recent experimental phenomena of hydrogen retention in the tungsten alloy and further recommends a suitable W–Re–Ta ternary alloy for possible plasma-facing materials (PFMs) including the consideration of the hydrogen retention.

  17. Hydrogen as an Indicator to Assess Biological Activity During Trace-Metal Bioremediation

    SciTech Connect

    Jaffe, Peter R.; Lovley, Derek; Komlos, John; Brown, Derick

    2004-03-17

    The design and operation of a trace-metal or radionuclide bioremediation scheme requires that specific redox conditions be achieved at given zones of an aquifer for a pre-determined duration. Tools are therefore needed to identify and quantify the terminal electron accepting processes (TEAPs) that are being achieved during bioremediation in an aquifer, and that this be done at a high spatial resolution. Dissolved hydrogen (H{sub 2}) concentrations have been shown to correlate with specific TEAPs during bioremediation in an aquifer (Table 1). Theoretical analysis has shown that these steady-state hydrogen levels are solely dependent upon the physiological parameters of the hydrogen-consuming microorganisms, with hydrogen concentrations increasing as each successive TEAP yields less energy for bacterial growth. The assumptions for this statement may not hold during a bioremediation scheme in which an organic substrate is injected into the subsurface and where organisms may consume hydrogen and carbon simultaneously. This research examines the effects of simultaneous hydrogen and carbon utilization through obtaining kinetic parameters of both hydrogen and carbon consumption under iron reducing conditions in batch experiments. A dual-donor model was formulated and compared to flow-through column experiments.

  18. Characterization and high throughput analysis of metal hydrides for hydrogen storage

    NASA Astrophysics Data System (ADS)

    Barcelo, Steven James

    Efficient hydrogen storage is required for fuel cell vehicles to be competitive with those driven by internal combustion engines. Current methods of storage such as compressed gas and liquid hydrogen cannot meet this standard, so novel hydrogen storage materials such as metal hydrides are required. No simple metal hydride meets the required specifications. Research is required to find new materials or improve existing materials. This thesis describes the research practices necessary to achieve legitimate and repeatable results in laboratories across the world. Examples of experiments using these techniques are presented, such as a high throughput technique to optimize materials systems with up to three components such as calcium borohydride with titanium catalyst and magnesium hydride with nickel and aluminum as destabilizing elements and catalysts. Thin films composed of gradients of each material were deposited by sputtering, creating a single thin film sample covering all potential material combinations. Optical properties of the samples under hydrogen pressure were monitored to identify the regions with largest and fastest hydrogen uptake. In the Ca-B-Ti system, titanium did not sufficiently catalyze the borohydride formation reaction at low temperature. Substantial hydrogen uptake was shown in the Mg-Ni region of the Mg-Ni-Al films. Al did not participate in the reaction at low temperature. Further investigation of the role of catalysts and destabilizing elements in improving hydrogen storage performance through X-ray Absorption and Emission Spectroscopy measurements of the Mg-Ni system during hydrogenation is presented. Typical X-ray spectroscopy measurements use a synchrotron radiation source and require ultra high vacuum conditions. For these experiments we designed a chamber which can be inserted into a vacuum chamber allowing in situ measurements of a sample under hydrogen pressure, providing information on the role of Ni in hydrogen absorption of Mg-Ni mixtures. Finally, another technique for improving hydrogen storage performance is presented which focuses on promising materials studied using the high throughput technique. TiO2 powder was ball milled together with NaBH 4, and gravimetric analysis shows a 50% improvement in the kinetics of the hydrogen desorption reaction and a reduction in desorption temperature of 60C.

  19. Influence of surface contaminations on the hydrogen storage behaviour of metal hydride alloys.

    PubMed

    Schülke, Mark; Paulus, Hubert; Lammers, Martin; Kiss, Gábor; Réti, Ferenc; Müller, Karl-Heinz

    2008-03-01

    Hydrogen storage in metal hydrides is a promising alternative to common storage methods. The surface of a metal hydride plays an important part in the absorption of hydrogen, since important partial reaction steps take place here. The development of surface contaminations and their influence on hydrogen absorption is examined by means of absorption experiments and surface analysis, using X-ray photoelectron spectroscopy (XPS), thermal desorption mass spectrometry (TDMS) and secondary neutral mass spectrometry (SNMS), in this work. All investigations were carried out on a modern AB(2) metal hydride alloy, namely Ti(0.96)Zr(0.04)Mn(1.43)V(0.45)Fe(0.08). Surface analysis (SNMS, XPS) shows that long-term air storage (several months) leads to oxide layers about 15 nm thick, with complete oxidation of all main alloy components. By means of in situ oxygen exposure at room temperature and XPS analysis, it can be shown that an oxygen dose of about 100 Langmuirs produces an oxide layer comparable to that after air storage. Manganese enrichment (segregation) is also clearly observed and is theoretically described here. This oxide layer hinders hydrogen absorption, so an activation procedure is necessary in order to use the full capacity of the metal hydride. This procedure consists of heating (T = 120 degrees C) in vacuum and hydrogen flushing at pressures like p = 18 bar. During the activation process the alloy is pulverized to particles of approximately 20 microm through lattice stretches. It is shown that this pulverization of the metal hydride (creating clean surface) during hydrogen flushing is essential for complete activation of the material. Re-activation of powder contaminated by small doses of air (p approximately 0.1 bar) does not lead to full absorption capacity. In ultrahigh vacuum, hydrogen is only taken up by the alloy after sputtering of the surface (which is done in order to remove oxide layers from it), thus creating adsorption sites for the hydrogen. This is shown by TDMS measurements with and without sputtering and oxygen exposure. PMID:18210095

  20. Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization.

    PubMed

    Zheng, Hong-Xing; Xiao, Zu-Feng; Yao, Chuan-Zhi; Li, Qiang-Qiang; Ning, Xiao-Shan; Kang, Yan-Biao; Tang, Yong

    2015-12-18

    Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments. PMID:26618248

  1. Experimental design and simulation of a metal hydride hydrogen storage system

    NASA Astrophysics Data System (ADS)

    Gadre, Sarang Ajit

    Metal hydrides, as a hydrogen storage medium, have been under consideration for many years because they have the ability to store hydrogen reversibly in the solid state at relatively low pressures and ambient temperatures. The utility of metal hydrides as a hydrogen storage medium was demonstrated recently by the Savannah River Technology Center (SRTC) in an on-board hydrogen storage system for a hybrid electric bus project. The complex geometry and the intricate design of the SRTC bed presents quite a challenge to the development of a mathematical model that can be used for design and optimization. In a new approach introduced here, the reversible reaction kinetics and the empirical Van't Hoff relationship used in a typical reactor model are replaced by a solid phase diffusion equation and one of the two semi-empirical equilibrium P-C-T relationships based on modified virial and composite Langmuir isotherm expressions. Starting with the simplest mathematical formulation, which resulted in an analytical expression, various models were developed and successively improved by relaxing certain assumptions, eventually resulting in the most rigorous model yet developed for this system. All of these models were calibrated using experimental pressure and temperature histories obtained from a bench scale hydrogen storage test facility. The heat and mass transfer coefficients or the thermal conductivity were the only adjustable parameters in these models. A design of experiments approach was also used for studying the effect of various factors on the performance of this bench scale hydrogen storage unit. Overall, the results of this study demonstrated that even a fairly simple numerical model could do a reasonable job in predicting the discharge behavior of a fairly complicated, metal hydride hydrogen storage bed over a wide range of operating conditions. The more rigorous 2-D model gave considerable insight into the dynamics of the hydrogen discharge process from an internal geometric design point of view. At the same time, the statistical design of experiments approach was shown to be a very efficient technique for identifying the most important process parameters that affect the performance of the metal hydride hydrogen storage unit with minimal experimental effort.

  2. Partial and complete reduction of O2 by hydrogen on transition metal surfaces

    SciTech Connect

    Ford, Denise; Nilekar, Anand Udaykumar; Xu, Ye; Mavrikakis, Manos

    2010-01-01

    The metal-catalyzed reduction of di-oxygen (O{sub 2}) by hydrogen is at the heart of direct synthesis of hydrogen peroxide (HOOH) and power generation by proton exchange membrane fuel cells. Despite its apparent simplicity, how the reaction proceeds on different metals is not yet well understood. We present a systematic study of O{sub 2} reduction on the (111) facets of eight transition metals (Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au) based on periodic density functional theory (DFT-GGA) calculations. Analysis of ten surface elementary reaction steps suggests three selectivity regimes as a function of the binding energy of atomic oxygen (BEO), delineated by the opposite demands to catalyze O-O bond scission and O-H bond formation: The dissociative adsorption of O{sub 2} prevails on Ni, Rh, Ir, and Cu; the complete reduction to water via associative (peroxyl, peroxide, and aquoxyl) mechanisms prevails on Pd, Pt, and Ag; and HOOH formation prevails on Au. The reducing power of hydrogen is decreased electrochemically by increasing the electrode potential. This hinders the hydrogenation of oxygen species and shifts the optimal selectivity for water to less reactive metals. Our results point to the important role of the intrinsic reactivity of metals in the selectivity of O{sub 2} reduction, provide a unified basis for understanding the metal-catalyzed reduction of O{sub 2} to H{sub 2}O and HOOH, and offer useful insights for identifying new catalysts for desired oxygen reduction products.

  3. Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction.

    PubMed

    Shi, Yanmei; Zhang, Bin

    2016-03-14

    The urgent need of clean and renewable energy drives the exploration of effective strategies to produce molecular hydrogen. With the assistance of highly active non-noble metal electrocatalysts, electrolysis of water is becoming a promising candidate to generate pure hydrogen with low cost and high efficiency. Very recently, transition metal phosphides (TMPs) have been proven to be high performance catalysts with high activity, high stability, and nearly ∼100% Faradic efficiency in not only strong acidic solutions, but also in strong alkaline and neutral media for electrochemical hydrogen evolution. In this tutorial review, an overview of recent development of TMP nanomaterials as catalysts for hydrogen generation with high activity and stability is presented. The effects of phosphorus (P) on HER activity, and their synthetic methods of TMPs are briefly discussed. Then we will demonstrate the specific strategies to further improve the catalytic efficiency and stability of TMPs by structural engineering. Making use of TMPs as cocatalysts and catalysts in photochemical and photoelectrochemical water splitting is also discussed. Finally, some key challenges and issues which should not be ignored during the rapid development of TMPs are pointed out. These strategies and challenges of TMPs are instructive for designing other high-performance non-noble metal catalysts. PMID:26806563

  4. Dissolution of Uranium Metal Without Hydride Formation or Hydrogen Gas Generation

    SciTech Connect

    Soderquist, Chuck Z.; Oliver, Brian M.; McNamara, Bruce K.

    2008-09-01

    This study shows that metallic uranium will cleanly dissolve in carbonate-peroxide solution without generation of hydrogen gas or uranium hydride. Metallic uranium shot, 0.5 to 1 mm diameter, were reacted with ammonium carbonate - hydrogen peroxide solution ranging in concentration from 0.13M to 1.0M carbonate and 0.50M to 2.0M peroxide. The uranium beads were weighed before and after reacting with the etch solution, and from the weights of the beads, their diameters were calculated, before and after the etch. The etch rate on the beads was then calculated from the reduction in bead diameter, and independently by uranium analysis of the solution. The calculated etch rate ranged from about 4 x 10-4 to 8 x 10-4 cm per hour, dependent primarily on the peroxide concentration. A hydrogen analysis of the etched beads showed that no detectable hydrogen was introduced into the uranium metal by the etching process.

  5. Functionalization of carbon-based nanostructures with light transition-metal atoms for hydrogen storage

    NASA Astrophysics Data System (ADS)

    Durgun, E.; Ciraci, S.; Yildirim, T.

    2008-02-01

    In a recent letter [T. Yildirim and S. Ciraci, Phys. Rev. Lett. 94, 175501 (2005)], the unusual hydrogen storage capacity of Ti decorated carbon nanotubes has been revealed. The present paper extends this study further to investigate the hydrogen uptake by light transition-metal atoms decorating various carbon-based nanostructures in different types of geometry and dimensionality, such as carbon linear chain, graphene, and nanotubes. Using first-principles plane-wave method we show that not only outer but also inner surface of a large carbon nanotube can be utilized to bind more transition-metal atoms and hence to increase the storage capacity. We also found that scandium and vanadium atoms adsorbed on a carbon nanotube can bind up to five hydrogen molecules. Similarly, light transition-metal atoms can be adsorbed on both sides of graphene and each adsorbate can hold up to four hydrogen molecules yielding again a high-storage capacity. Interestingly, our results suggest that graphene can be considered as a potential high-capacity H2 storage medium. We also performed transition state analysis on the possible dimerization of Ti atoms adsorbed on the graphene and single-wall carbon nanotube.

  6. Functional isocyanide metal complexes as building blocks for supramolecular materials: hydrogen-bonded liquid crystals.

    PubMed

    Coco, Silverio; Espinet, Elisa; Espinet, Pablo; Palape, Inés

    2007-08-14

    Gold, palladium and platinum complexes with an unusual isocyanide ligand containing a carboxylic acid function, [AuCl(CNC(6)H(4)COOH)], cis-[MI(2)(CNC(6)H(4)COOH)(2)] and trans-[MI(2)(CNC(6)H(4)COOH)(2)] (M = Pd, Pt) have been isolated. The carboxylic acid group of the coordinated isocyanide acts as a hydrogen donor for hydrogen-bonding and three series of stable hydrogen-bonded liquid crystalline metal complexes have been prepared with decyloxystilbazole. Although all the metal acid derivatives used are not mesomorphic, and decyloxystilbazole only shows an ordered Smectic E phase, four out of the five hydrogen-bonded decyloxystilbazole complexes studied display enantiotropic smectic A or nematic mesophases. The single crystal X-ray diffraction structure of trans-[PdI(2)(CNC(6)H(4)COOH)(2)].C(4)H(8)O(2) has been determined and confirms the formation of a supramolecular array in the solid state supported by hydrogen-bonding. PMID:17893772

  7. Hydrogen Spillover between Single Gold Nanorods and Metal Oxide Supports: A Surface Plasmon Spectroscopy Study.

    PubMed

    Collins, Sean S E; Cittadini, Michela; Pecharromn, Carlos; Martucci, Alessandro; Mulvaney, Paul

    2015-08-25

    We used dark field spectroscopy to monitor the dissociation of hydrogen on single gold nanoparticles embedded in metal oxide supports. Individual gold nanorods were monitored in real time to reveal the peak position, the full width at half-maximum, and the relative intensity of the surface plasmon resonances during repeated N2-H2-N2 and air-H2-air cycles. Shifts in the spectra are shown to be due to changes in electron density and not to refractive index shifts in the environment. We demonstrate that hydrogen does not dissociate on gold nanorods (13 nm 40 nm) at room temperature when in contact with silica and that electrons or hydrogen atoms migrate from Pt nanoparticles to Au nanoparticles through the supporting metal oxide at room temperature. However, this spillover mechanism only occurs for semiconducting oxides (anatase TiO2 and ZnO) and does not occur for Au and Pt nanoparticles embedded in silica. Finally, we show that hydrogen does dissociate directly on anatase surfaces at room temperature during air-H2-air cycles. Our results show that hydrogen spillover, surface dissociation of reactants, and surface migration of chemical intermediates can be detected and monitored in real time at the single particle level. PMID:26154166

  8. First-principles study of hydrogen adsorption in metal-doped COF-10

    SciTech Connect

    Wu Miaomiao; Sun Qiang; Wang Qian; Jena, Puru; Kawazoe, Yoshiyuki

    2010-10-21

    Covalent organic frameworks (COFs), due to their low-density, high-porosity, and high-stability, have promising applications in gas storage. In this study we have explored the potential of COFs doped with Li and Ca metal atoms for storing hydrogen under ambient thermodynamic conditions. Using density functional theory we have performed detailed calculations of the sites Li and Ca atoms occupy in COF-10 and their interaction with hydrogen molecules. The binding energy of Li atom on COF-10 substrate is found to be about 1.0 eV and each Li atom can adsorb up to three H{sub 2} molecules. However, at high concentration, Li atoms cluster and, consequently, their hydrogen storage capacity is reduced due to steric hindrance between H{sub 2} molecules. On the other hand, due to charge transfer from Li to the substrate, O sites provide additional enhancement for hydrogen adsorption. With increasing concentration of doped metal atoms, the COF-10 substrate provides an additional platform for storing hydrogen. Similar conclusions are reached for Ca doped COF-10.

  9. The Role of Water in the Storage of Hydrogen in Metals

    NASA Technical Reports Server (NTRS)

    Hampton, Michael D.; Lomness, Janice K.; Giannuzzi, Lucille A.

    2001-01-01

    One major problem with the use of hydrogen is safe and efficient storage. In the pure form, bulky and heavy containers are required greatly reducing the efficiency of its use. Safety is also a great concern. Storage of hydrogen in the form of a metal hydride offers distinct advantages both in terms of volumetric efficiency and in terms of safety. As a result, an enormous amount of research is currently being done on metal-hydrogen systems. Practical application of these systems to storage of hydrogen can only occur when they are very well understood. In this paper, the preliminary results of a study of the surfaces of magnesium nickel alloys will be presented. Alloys that have been rendered totally unreactive with hydrogen as well as those that have been activated with liquid water and with water vapor were studied. Data obtained from XPS (X-ray Photoelectron Spectrometer) analysis, with samples held in vacuum for the shortest possible time to minimize the hydroxide degradation will be presented. Furthermore, TEM data on samples prepared in a new way that largely protects the surface from the high vacuum will be discussed.

  10. Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

    PubMed

    Zell, Thomas; Milstein, David

    2015-07-21

    The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in some cases can even exceed those of state-of-the-art noble-metal catalysts. For the iron PNP systems, we describe the synthesis of the pyridine- and acridine-based PNP iron complexes and their performances and limitations in catalytic reactions, and we present studies on their reactivity with relevance to their catalytic mechanisms. In the case of the bipyridine-based PNN system, we summarize the synthesis of new complexes and describe studies on the noninnocence of the methylene position, which can be reversibly deprotonated, as well as on the noninnocence of the bipyridine unit. Overall, this Account underlines that the combination of cheap and abundant iron with ligands that are capable of metal-ligand cooperation can result in the development of novel, versatile, and efficient catalysts for atom-efficient catalytic reactions. PMID:26079678

  11. Cold three-body collisions in hydrogen-hydrogen-alkali-metal atomic systems

    SciTech Connect

    Wang Yujun; Esry, B. D.; D'Incao, J. P.

    2011-03-15

    We have studied hydrogen-hydrogen-alkali three-body systems in the adiabatic hyperspherical representation. For the spin-stretched case, there exists a single XH molecular state when X is one of the bosonic alkali atoms: {sup 7}Li, {sup 23}Na, {sup 39}K, {sup 87}Rb, or {sup 133}Cs. As a result, the only recombination process is the one that leads to formation of XH molecules, H+H+X{yields}XH+H, and such molecules will be stable against vibrational relaxation. We have calculated the collision rates for recombination and collision-induced dissociation as well as the elastic cross sections for H+XH collisions up to a temperature of 0.5 K, including the partial wave contributions from J{sup {Pi}=}0{sup +} to 5{sup -}. We have also found that there is just one three-body bound state for such systems for J{sup {Pi}=}0{sup +} and no bound states for higher angular momenta.

  12. First principles assessment of ideal fracture energies of materials with mobile impurities: implications for hydrogen embrittlement of metals

    SciTech Connect

    Jiang, D.E.; Carter, Emily A. . E-mail: eac@chem.ucla.edu

    2004-09-20

    We propose that the ideal fracture energy of a material with mobile bulk impurities can be obtained within the framework of a Born-Haber thermodynamic cycle. We show that such a definition has the advantage of initial and final states at equilibrium, connected by well-defined and measurable energetic quantities, which can also be calculated from first principles. Using this approach, we calculate the ideal fracture energy of metals (Fe and Al) in the presence of varying amounts of hydrogen, using periodic density functional theory. We find that the metal ideal fracture energy decreases almost linearly with increasing hydrogen coverage, dropping by {approx}45% at one-half monolayer of hydrogen, indicating a substantial reduction of metal crystal cohesion in the presence of hydrogen atoms and providing some insight into the cohesion-reduction mechanism of hydrogen embrittlement in metals.

  13. Minimum metallic conductivity of fluid hydrogen at 140 GPa (1.4 Mbar)

    SciTech Connect

    Nellis, W.J.; Weir, S.T.; Mitchell, A.C.

    1999-02-01

    Electrical conductivity measurements indicate that fluid hydrogen achieves the minimum conductivity of a metal at 140 GPa, ninefold initial liquid-H{sub 2} density, and 2600 K. Metallization density is defined to be that at which the electronic mobility gap E{sub g} is reduced by pressure to E{sub g}{approximately}k{sub B}T, at which point E{sub g} is filled in by fluid disorder to produce a metallic density of states with a Fermi surface and the minimum conductivity of a metal. High pressures and temperatures were obtained with a two-stage gun, which accelerates an impactor up to 7 km/sec. A strong shock wave is generated on impact with a holder containing liquid hydrogen at 20 K. The impact shock is split into a shock wave reverberating in hydrogen between two stiff Al{sub 2}O{sub 3} anvils. This compression heats hydrogen quasi-isentropically to about twice its melting temperature and lasts {approximately}100 ns, sufficiently long to achieve equilibrium and sufficiently short to preclude loss of hydrogen by diffusion and chemical reactions. The measured conductivity increases four orders of magnitude in the range 93 to 140 GPa and is constant at 2000 ({Omega}&hthinsp;cm){sup {minus}1} from 140 to 180 GPa. This conductivity is that of fluid Cs and Rb undergoing the same transition at 2000 K. This measured value is within a factor of 5 or less of hydrogen conductivities calculated with (i) minimum conductivity of a metal, (ii) Ziman model of a liquid metal, and (iii) tight-binding molecular dynamics. At metallization this fluid is {approximately}90 at.&hthinsp;{percent} H{sub 2} and 10 at.&hthinsp;{percent} H with a Fermi energy of {approximately}12 eV. Fluid hydrogen at finite temperature undergoes a Mott transition at D{sub m}{sup 1/3}a{sup {asterisk}}=0.30, where D{sub m} is the metallization density and a{sup {asterisk}} is the Bohr radius of the molecule. Metallization occurs at a lower pressure in the fluid than predicted for the solid probably because crystalline and orientational phase transitions in the ordered solid do not occur in the fluid and because of many-body and structural effects. Tight-binding molecular dynamics calculations by Lenosky {ital et al.} suggest that fluid metallic hydrogen is a novel state of condensed matter. Protons are paired transiently and exchange on a timescale of a few molecular vibrational periods, {approximately}10{sup {minus}14}&hthinsp;sec. Also, the kinetic, vibrational, and rotational energies of the dynamically paired protons are comparable. {copyright} {ital 1999} {ital The American Physical Society}

  14. Considerations for Storage of High Test Hydrogen Peroxide (HTP) Utilizing Non-Metal Containers

    NASA Technical Reports Server (NTRS)

    Moore, Robin E.; Scott, Joseph P.; Wise, Harry

    2005-01-01

    When working with high concentrations of hydrogen peroxide, it is critical that the storage container be constructed of the proper materials, those which will not degrade to the extent that container breakdown or dangerous decomposition occurs. It has been suggested that the only materials that will safely contain the peroxide for a significant period of time are metals of stainless steel construction or aluminum use as High Test Hydrogen Peroxide (HTP) Containers. The stability and decomposition of HTP will be also discussed as well as various means suggested in the literature to minimize these problems. The dangers of excess oxygen generation are also touched upon.

  15. SOLUBILITY OF WATER ICE IN METALLIC HYDROGEN: CONSEQUENCES FOR CORE EROSION IN GAS GIANT PLANETS

    SciTech Connect

    Wilson, H. F.; Militzer, B.

    2012-01-20

    Using ab initio simulations we investigate whether water ice is stable in the cores of giant planets, or whether it dissolves into the layer of metallic hydrogen above. By Gibbs free energy calculations we find that for pressures between 10 and 40 Mbar the ice-hydrogen interface is thermodynamically unstable at temperatures above approximately 3000 K, far below the temperature of the core-mantle boundaries in Jupiter and Saturn. This implies that the dissolution of core material into the fluid layers of giant planets is thermodynamically favored, and that further modeling of the extent of core erosion is warranted.

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

    NASA Astrophysics Data System (ADS)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bücherl, T.; Söllradl, S.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2015-10-01

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

  17. Metallization of hydrogen and the essential differences between dynamic and static compression

    NASA Astrophysics Data System (ADS)

    Nellis, W.

    2013-06-01

    In 1935 Wigner and Huntington (WH) predicted that at density DThry = 0.62 mole H/cm3, ``very low temperatures,'' and a pressure greater than 25 GPa, bcc H2 undergoes an isostructural phase transition directly to H with an associated insulator-metal transition (IMT). In 1996 metallic fluid H was made under dynamic compression in a cross over from H2 to H that completes at Dexp = 0.64 mole H/cm3, 140 GPa and T ~ 2600 K. The Free-electron Fermi temperature TF = 220,000 K and T/TF = 0.012 << 1 , as for ordinary metals at 300 K. To date solid metallic hydrogen has yet to be made at static pressures up to ~360 GPa at T ~ 300 K. This difference between electrical conductivity of H2 compressed dynamically and statistically begs the question of why fluid H at 140 GPa and ~3000 K becomes metallic at 0.64 mol H/cm3, the density predicted by WH for their IMT at low T; whereas metallization of solid H2 or H near 300 K is yet to be achieved experimentally at pressures up to ~360 GPa? The answer is systematic differences induced by the rate of application of pressure in the two methods. Slow compression at ~300 K strengthens solid H2 by inducing intermolecular bonds, which impede dissociation, metallization and perhaps even thermal equilibrium. Fast dynamic compression of liquid H2 up to ~3000 K precludes formation of intermolecular H-H bonds, which permits fluid H2 to weaken to dissociation and thus metallization at 140 GPa. Dynamic- and static-compression effects on materials will be compared in the context of how they effect metallization of hydrogen.

  18. Reverse hydrogen spillover in supported subnanosize clusters of the metals of groups 8 to 11. A computational model study.

    PubMed

    Vayssilov, Georgi N; Rsch, Notker

    2005-12-01

    In a recent computational study [G. N. Vayssilov, B. C. Gates and N. Rsch, Angew. Chem., Int. Ed. Eng., 2003, 42, 1391], we found zeolite-supported Rh6 clusters, interacting with hydroxyl groups of the support, to undergo partial oxidation due to reverse spillover of hydrogen onto the metal cluster. Now, we have extended this model study to transition metal clusters M6 of the platinum and gold groups. According to the model calculations, reverse spillover of hydrogen onto the zeolite-supported metal clusters is energetically favored for all 12 metals. For most metals, the clusters M6 exhibit a compact form in either of the two states--bare supported and with hydrogen impurities. However, for Cu and Ag, the structures of the clusters with H impurities were determined to be more open, whereas Au6 exhibited an almost planar structure in either state. The estimated energy for reverse hydrogen spillover is lowest for the clusters Au6 and Ag6, 18 and 52 kJ mol(-1) per transferred hydrogen, and highest for the clusters Ir6 and Os6, 229 and 247 kJ mol(-1), respectively. Because of these model results, one would expect small metal clusters, supported on OH covered surfaces, likely to be oxidized and partially covered by hydrogen, substantially affecting the electron distribution and the chemical reactivity of the clusters. To assist in the experimental discrimination of hydrogen impurities of adsorbed metal clusters, we propose two criteria: metal core levels are predicted to be stabilized in the case of reverse hydrogen spillover and the number of metal-oxygen contacts is calculated to be twice as large in clusters with hydrogen impurities. PMID:19810333

  19. DIRECT DECOMPOSITION OF METHANE TO HYDROGEN ON METAL LOADED ZEOLITE CATALYST

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Kyle C. Burch; Harry W. Rollins

    2005-08-01

    The manufacture of hydrogen from natural gas is essential for the production of ultra clean transportation fuels. Not only is hydrogen necessary to upgrade low quality crude oils to high-quality, low sulfur ultra clean transportation fuels, hydrogen could eventually replace gasoline and diesel as the ultra clean transportation fuel of the future. Currently, refinery hydrogen is produced through the steam reforming of natural gas. Although efficient, the process is responsible for a significant portion of refinery CO2 emissions. This project is examining the direct catalytic decomposition of methane as an alternative to steam reforming. The energy required to produce one mole of hydrogen is slightly lower and the process does not require water-gas-shift or pressure-swing adsorption units. The decomposition process does not produce CO2 emissions and the product is not contaminated with CO -- a poison for PEM fuel cells. In this work we examined the direct catalytic decomposition of methane over a metal modified zeolite catalyst and the recovery of catalyst activity by calcination. A favorable production of hydrogen was obtained, when compared with previously reported nickel-zeolite supported catalysts. Reaction temperature had a strong influence on catalyst activity and on the type of carbon deposits. The catalyst utilized at 873 and 973 K could be regenerated without any significant loss of activity, however the catalyst utilized at 1073 K showed some loss of activity after regeneration.

  20. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    NASA Astrophysics Data System (ADS)

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-02-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.

  1. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    PubMed Central

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-01-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. PMID:26902901

  2. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage.

    PubMed

    Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J

    2016-01-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. PMID:26902901

  3. Cleavage of hydrogen by activation at a single non-metal centre - towards new hydrogen storage materials.

    PubMed

    Grabowski, S?awomir J

    2015-05-28

    Molecular surfaces of non-metal species are often characterized by both positive and negative regions of electrostatic potential (EP) at a non-metal centre. This centre may activate molecular hydrogen which further leads to the addition reaction. The positive EP regions at the non-metal centres correspond to ?-holes; the latter sites are enhanced by electronegative substituents. This is why the following simple moieties; PFH2, SFH, AsFH2, SeFH, BrF3, PF(CH3)2 and AsF(CH3)2, were chosen here to analyze the H2 activation and its subsequent splitting at the P, As, S, Se and Br centres. Also the reverse H-H bond reforming process is analyzed. MP2/aug-cc-pVTZ calculations were performed for systems corresponding to different stages of these processes. The sulphur centre in the SFH moiety is analyzed in detail since the potential barrier height for the addition reaction for this species is the lowest of the moieties analyzed here. The results of calculations show that the SFH + H2 ? SFH3 reaction in the gas phase is endothermic but it is exothermic in polar solvents. PMID:25939477

  4. Recyclable Earth-Abundant Metal Nanoparticle Catalysts for Selective Transfer Hydrogenation of Levulinic Acid to Produce ?-Valerolactone.

    PubMed

    Gowda, Ravikumar R; Chen, Eugene Y-X

    2016-01-01

    Nanoparticles (NPs) derived from earth-abundant metal(0) carbonyls catalyze conversion of bio-derived levulinic acid into ?-valerolactone in up to 93?% isolated yield. This sustainable and green route uses non-precious metal catalysts and can be performed in aqueous or ethanol solution without using hydrogen gas as the hydrogen source. Generation of metal NPs using microwave irradiation greatly enhances the rate of the conversion, enables the use of ethanol as both solvent and hydrogen source without forming the undesired ethyl levulinate, and affords recyclable polymer-stabilized NPs. PMID:26735911

  5. Metal doped carbon nanoneedles and effect of carbon organization with activity for hydrogen evolution reaction (HER).

    PubMed

    Araujo, Rafael A; Rubira, Adley F; Asefa, Tewodros; Silva, Rafael

    2016-02-10

    Cellulose nanowhiskers (CNW) from cotton, was prepared by acid hydrolysis and purified using a size selection process to obtain homogeneous samples with average particle size of 270nm and 85.5% crystallinity. Purified CNW was used as precursor to carbon nanoneedles (CNN) synthesis. The synthesis of CNN loaded with different metals dopants were carried out by a nanoreactor method and the obtained CNNs applied as electrocatalysts for hydrogen evolution reaction (HER). In the carbon nanoneedles synthesis, Ni, Cu, or Fe worked as graphitization catalyst and the metal were found present as dopants in the final material. The used metal appeared to have direct influence on the degree of organization of the particles and also in the surface density of polar groups. It was evaluated the influence of the graphitic organization on the general properties and nickel was found as the more appropriate metal since it leads to a more organized material and also to a high activity toward HER. PMID:26686184

  6. Hydrogen storage properties of light metal adatoms (Li, Na) decorated fluorographene monolayer.

    PubMed

    Hussain, T; Islam, M S; Rao, G S; Panigrahi, P; Gupta, D; Ahuja, Rajeev

    2015-07-10

    Owing to its high energy density, the potential of hydrogen (H2) as an energy carrier has been immense, however its storage remains a big obstacle and calls for an efficient storage medium. By means of density functional theory (DFT) in spin polarized generalized gradient approximation (GGA), we have investigated the structural, electronic and hydrogen storage properties of a light alkali metal (Li, Na) functionalized fluorographene monolayer (FG). Metal adatoms bind to the FG with significantly high binding energy, much higher than their cohesive energies, which helps to achieve a uniform distribution of metal adatoms on the monolayer and consequently ensure reversibility. Due to a difference of electronegativities, each metal adatom transfers a substantial amount of its charge to the FG monolayer and attains a partial positive state, which facilitates the adsorption of multiple H2 molecules around the adatoms by electrostatic as well as van der Waals interactions. To get a better description of H2 adsorption energies with metal-doped systems, we have also performed calculations using van der Waals corrections. For both the functionalized systems, the results indicate a reasonably high H2 storage capacity with H2 adsorption energies falling into the range for the practical applications. PMID:26066734

  7. Hall effect in Zr-Ni and Zr-Cu metallic glasses doped with hydrogen

    SciTech Connect

    Kokanovic, I.; Leontic, B. ); Lukatela, J.; Ivkov, J. )

    1990-12-15

    We have studied the effect of hydrogen doping on the Hall resistivity of paramagnetic Zr{sub 76}Ni{sub 24}, Zr{sub 40}Ni{sub 60}, Zr{sub 70}Cu{sub 30}, and Zr{sub 60}Cu{sub 40} metallic glasses. All the alloys have positive Hall coefficients except the Zr{sub 40}Ni{sub 60}. The hydrogen dopant increases the absolute value of the Hall coefficient irrespective of its sign, except in the case of (Zr{sub 70}Cu{sub 30}){sub 1{minus}{ital x}}H{sub {ital x}}, where the Hall coefficient decreases for low hydrogen concentrations ({ital x}{lt}0.04) and increases at higher ones, while staying positive all the time. The results are explained as being due to the enhanced {ital s}-{ital d} hybridization.

  8. Study on monatomic fraction improvement with alumina layer on metal electrode in hydrogen plasma ion source

    SciTech Connect

    Jung, Bong-Ki; Chung, Kyoung-Jae; Dang, Jeong-Jeung; Hwang, Y. S.

    2012-02-15

    A high monatomic beam fraction is an important factor in a hydrogen ion source to increase the application efficiency. The monatomic fraction of hydrogen plasmas with different plasma electrode materials is measured in a helicon plasma ion source, and aluminum shows the highest value compared to that with the other metals such as copper and molybdenum. Formation of an aluminum oxide layer on the aluminum electrode is determined by XPS analysis, and the alumina layer is verified as the high monatomic fraction. Both experiments and numerical simulations conclude that a low surface recombination coefficient of the alumina layer on the plasma electrode is one of the most important parameters for increasing the monatomic fraction in hydrogen plasma ion sources.

  9. Computational modeling of the mechanism of hydrogen embrittlement (HE) and stress corrosion cracking (SCC) in metals

    NASA Astrophysics Data System (ADS)

    Cendales, E. D.; Orjuela, F. A.; Chamarraví, O.

    2016-02-01

    In this article theoretical models and some existing data sets were examined in order to model the two main causes (hydrogen embrittlement and corrosion-cracking under stress) of the called environmentally assisted cracking phenomenon (EAC). Additionally, a computer simulation of flat metal plate subject to mechanical stress and cracking due both to hydrogen embrittlement and corrosion was developed. The computational simulation was oriented to evaluate the effect on the stress-strain behavior, elongation percent and the crack growth rate of AISI SAE 1040 steel due to three corrosive enviroments (H2 @ 0.06MPa; HCl, pH=1.0; HCl, pH=2.5). From the computer simulation we conclude that cracking due to internal corrosion of the material near to the crack tip limits affects more the residual strength of the flat plate than hydrogen embrittlement and generates a failure condition almost imminent of the mechanical structural element.

  10. Cryogenic Gellant and Fuel Formulation for Metallized Gelled Propellants: Hydrocarbons and Hydrogen with Aluminum

    NASA Technical Reports Server (NTRS)

    Wong, Wing; Starkovich, John; Adams, Scott; Palaszewski, Bryan; Davison, William; Burt, William; Thridandam, Hareesh; Hu-Peng, Hsiao; Santy, Myrrl J.

    1994-01-01

    An experimental program to determine the viability of nanoparticulate gellant materials for gelled hydrocarbons and gelled liquid hydrogen was conducted. The gellants included alkoxides (BTMSE and BTMSH) and silica-based materials. Hexane, ethane, propane and hydrogen were gelled with the newly-formulated materials and their rheological properties were determined: shear stress versus shear rate and their attendant viscosities. Metallized hexane with aluminum particles was also rheologically characterized. The propellant and gellant formulations were selected for the very high surface area and relatively-high energy content of the gellants. These new gellants can therefore improve rocket engine specific impulse over that obtained with traditional cryogenic-fuel gellant materials silicon dioxide, frozen methane, or frozen ethane particles. Significant reductions in the total mass of the gellant were enabled in the fuels. In gelled liquid hydrogen, the total mass of gellant was reduced from 10-40 wt percent of frozen hydrocarbon particles to less that 8 wt percent with the alkoxide.

  11. Hydrogen-induced metallicity and strengthening of MoS2

    NASA Astrophysics Data System (ADS)

    Yakovkin, I. N.; Petrova, N. V.

    2014-04-01

    The performed DFT calculations for MoS2 layers with adsorbed and intercalated hydrogen indicate that the atomic hydrogen monolayer makes the surface metallic. The physisorbed H2 does not affect electronic properties of the MoS2 monolayer, which remains a direct gap semiconductor. Due to forming S-H-S bonds, hydrogen atoms, intercalated into the space between MoS2 layers, increase the interlayer interaction from 0.12 eV to 0.60 eV. The related increase of the stiffness of the Mo-H-Mo layered system is of a primary importance for the interpretation of images of the surface obtained with the Ultrasonic Force Microscopy (Kolosov and Yamanaka, 1993) [42].

  12. Ab initio study of adsorption of molecular hydrogen on microporous metal-organic frameworks.

    NASA Astrophysics Data System (ADS)

    Hamel, Sbastien; Ct, Michel

    2004-03-01

    In the ongoing search for promising compounds for hydrogen storage, novel porous metal-organic frameworks (MOF) have been discovered recently [1]. Well defined binding sites were deduced from inelastic neutron scattering (INS) spectroscopy of the rotational transitions of the adsorbed molecular hydrogen. In light of this discovery we performed ab initio density functional theory (DFT) calculations of the adsorption of molecular hydrogen on this class of microporous MOF to compare different adsorption sites. Different approximations for the exchange-correlation potentials were accessed for a set of relevant properties such as binding energy, energetically favored configuration and distance between the adsorbents and adsorbates. In particular, theoretical rotational spectra of the adsorbed H2 were obtained that could be compared to the experimental INS spectra. [1] Rosi et al., Science Vol. 300, 1127 (2003)

  13. Infrared reflectance measurements of the insulator-metal transition in solid hydrogen

    NASA Technical Reports Server (NTRS)

    Mao, H. K.; Hemley, R. J.; Hanfland, M.

    1990-01-01

    Reflectance measurements on solid hydrogen to 177 GPa (1.77 Mbar) have been performed from near-infrared to ultraviolet wavelengths (0.5 to 3 eV). Above 150 GPa characteristic free-electron behavior in the infrared region is observed to increase sharply with increasing pressure. Analysis of volume dependence of the plasma frequency obtained from Drude-model fits to the spectra indicates that the pressure of the insulator-metal transition is 149 (+ or - 10) GPa at 295 K. The measurements are consistent with metallization by closure of an indirect gap in the molecular solid.

  14. Simulation studies of a model of high-density metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Mon, K. K.; Chester, G. V.; Ashcroft, N. W.

    1980-01-01

    Upper bounds for the ground-state energies of liquid and solid phases of metallic hydrogen and metallic deuterium have been calculated with variational methods and Monte Carlo techniques. At four densities (0.8, 1.2, 1.36, and 1.488) crystalline phases are clearly preferred in the sense that the energy difference, when compared to the liquid, is in excess of the errors inherent in the numerical procedures. At a fifth density (1.6), the energy differences between solid and liquid phases are smaller than these errors.

  15. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water

    PubMed Central

    Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng; Wang, Hai Feng; Yang, Zhen Zhong; Zheng, Li Rong; Hu, P.; Zhao, Hui Jun; Gu, Lin; Yang, Hua Gui

    2015-01-01

    Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry. PMID:26286479

  16. Effect of metal and nonmetal on adsorption of hydrogen in torus-type C120

    NASA Astrophysics Data System (ADS)

    Zhou, Caihua; Ma, Ning; Fan, Guang; Ma, Zhanying

    2016-02-01

    The hydrogen adsorption properties for the torus-type C120, and the changes of adsorption influenced by nonmetal and metal have been systematically investigated. The results show that, in the pristine torus-type C120, the inner carbon atoms have more negative static potential than the outer ones. H2 intends to accumulate at the area near inner carbon atoms. However, torus-type C120 is modified by nonmetal (N and O) or metal (Li), the accumulated fields of H2 are changed. Li can evidently enhance the hydrogen storage capacity. The most gravimetric density is predicted to be 7.21 wt% for the 8Li-C120 in 77 K and 1200 kPa.

  17. Two-component Fermi-liquid theory - Equilibrium properties of liquid metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Oliva, J.; Ashcroft, N. W.

    1981-01-01

    It is reported that the transition of condensed hydrogen from an insulating molecular crystal phase to a metallic liquid phase, at zero temperature and high pressure, appears possible. Liquid metallic hydrogen (LMH), comprising interpenetrating proton and electron fluids, would constitute a two-component Fermi liquid with both a very high component-mass ratio and long-range, species-dependent bare interactions. The low-temperature equilibrium properties of LMH are examined by means of a generalization to the case of two components of the phenomenological Landau Fermi-liquid theory, and the low-temperature specific heat, compressibility, thermal expansion coefficient and spin susceptibility are given. It is found that the specific heat and the thermal expansion coefficient are vastly greater in the liquid than in the corresponding solid, due to the presence of proton quasiparticle excitations in the liquid.

  18. Anion Binding in Metal-Organic Frameworks Functionalized with Urea Hydrogen-Bonding Groups

    SciTech Connect

    Custelcean, Radu; Moyer, Bruce A; Bryantsev, Vyacheslav S.; Hay, Benjamin P.

    2006-01-01

    A series of metal-organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups has been synthesized and structurally analyzed by single-crystal X-ray diffraction to evaluate the efficacy of anion coordination by urea within the structural constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal-organic frameworks when the tendency for urea{hor_ellipsis}urea self-association is decreased by strengthening the intramolecular CH{hor_ellipsis}O hydrogen bonding of N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N'-bis(m-pyridyl)urea (BPU) and N,N'-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies to self-associate into hydrogen-bonded tapes compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO{sub 4}){sub 2}, ZnSO{sub 4}, Cu(NO{sub 3}){sub 2}, Cu(CF{sub 3}SO{sub 3}){sub 2}, AgNO{sub 3}, and AgSO{sub 3}CH{sub 3}. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion coordination by the urea functionalities was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate.

  19. On the lattice dynamics of metallic hydrogen and other Coulomb systems

    NASA Technical Reports Server (NTRS)

    Beck, H.; Straus, D.

    1975-01-01

    Numerical results for the phonon spectra of metallic hydrogen and other Coulomb systems in cubic lattices are presented. In second order in the electron-ion interaction, the behavior of the dielectric function of the interacting electron gas for arguments around the seond Fermi harmonic leads to drastic Kohn anomalies and even to imaginary phonon frequencies. Third-order band-structure corrections are also calculated. Properties of self-consistent phonons and the validity of the adiabatic approximation are discussed.

  20. Neutron and Thermodynamic Studies of Hydrogen on Pd Decorated Metal Oxides

    NASA Astrophysics Data System (ADS)

    Landry, Paige; Ramirez-Cuesta, A.; Cruz Silvia, E.; Sumpter, B.; Larese, J. Z.

    2011-03-01

    We report our investigations of thermodynamic, inelastic and quasielastic neutron scattering (INS and QENS) studies of H2 adsorbed on bare and Pd decorated metal oxide (MO) surfaces, specifically ZnO, SBA-15 silica, and alumina. Guided by our volumetric adsorption measurements, we used INS and QENS to probe the dynamics of the adsorbed hydrogen molecules. These measurements provide insight into how the microscopic behavior of hydrogen is changed when it is confined at interfaces or interacts with a Pd catalyst. Using INS, the motion of the adsorbed hydrogen are examined as a function of surface adsorbate composition. For rotational motion we use the ortho-to-para transition as a guide and find that the rotational barrier for H2 adsorbed on some of these MO surfaces shift to lower energy (relative to bulk H2). For comparison, the hydrogen adsorption and microscopic behavior when the MO are decorated with 1% Pd metal will be discussed. Evidence for the presence of adsorbed H2, Zn hydroxide and the potential role of spillover will be discussed. This work was partially supported by the U.S. DOE, BES under contract No. DE-AC05-00OR22725 with ORNL managed and operated by UT-Battelle, LLC, the NSF under grant DMR-0412231 and a grant from the University of Tennessee, JINS.

  1. Modelling of hydrogen adsorption in the metal organic framework MOF5

    NASA Astrophysics Data System (ADS)

    Mulder, F. M.; Dingemans, T. J.; Wagemaker, M.; Kearley, G. J.

    2005-10-01

    Metal organic frameworks are formed by rigid organic spacer molecules linked by metal ions into a three-dimensional nano porous structure. The large internal surface (up to 4500 m 2 g -1) provides abundant sites for the adsorption of small molecules like hydrogen, which currently generates significant interest for their potential application as reversible hydrogen storage matrix. A prerequisite for hydrogen storage at ambient conditions is that the interaction strength is sufficiently large. Using VASP ab initio computer calculations the adsorption interaction strength for MOF5 is found to be of the order of 70 meV per H 2 molecule, where the main adsorption interaction is with the oxygen atoms. Such value compares well with adsorption experiments on MOF5 and it exceeds that obtained in nanostructured pure carbon materials. The J = 0 to J = 1 rotational transition of the H 2 determined from inelastic neutron scattering results of Rosi et al. [N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, O.M. Yaghi, Science 300 (2003) 1127] is compared to the simulation results, and a hydrogen self diffusion coefficient is estimated.

  2. Retention of Hydrogen in FCC Metals Irradiated at Temperatures Leading to High Densities of Bubbles or Voids

    SciTech Connect

    Garner, Francis A.; Simonen, Edward P.; Oliver, Brian M.; Greenwood, Lawrence R.; Grossbeck, M L.; Wolfer, W. G.; Scott, P M.

    2006-09-15

    Large amounts of hydrogen and helium are generated in structural metals in accelerator-driven systems. It is shown that under certain conditions, hydrogen can be stored in irradiated nickel and stainless steels at levels strongly in excess of that predicted by Sieverts Law. These conditions are first, the availability of hydrogen from various radiolytic and environmental sources and second, the formation of radiation-induced cavities to store hydrogen. These cavities can be highly pressurized bubbles or under-pressurized voids, with concurrent helium in the cavities at either low or very high levels. Transmutant sources of hydrogen are often insufficient to pressurize these cavities, and therefore environmental sources are required. The stored hydrogen appears to be stable for many years at room temperature. A conceptual model to describe such behavior requires the continuous generation of hydrogen from (n, p) reactions and possibly other radiolytic sources which can create a supersaturation of hydrogen in the metal, leading to the pressurization of voids and helium bubbles. Once captured in a bubble, the hydrogen is assumed to be in molecular form. Dissolution back into the metal requires chemisorption and dissociation on the bubble surface. Both of these processes have large activation barriers, particularly when oxygen, carbohydrates, and other impurities poison the bubble surface. However, these chemisorbed poisons may reduce but not entirely restrict the ingress or egress of atomic hydrogen.

  3. HYDROGEN SEPARATION MEMBRANES

    SciTech Connect

    Donald P. McCollor; John P. Kay

    1999-08-01

    A likely membrane for future testing of high-temperature hydrogen separation from a gasification product stream was targeted as an inorganic analog of a dense-metal membrane, where the hydrogen would dissolve into and diffuse through the membrane structure. An amorphous membrane such as zinc sulfide appeared to be promising. Previously, ZnS film coating tests had been performed using an electron-beam vacuum coating instrument, with zinc films successfully applied to glass substrates. The coatings appeared relatively stable in air and in a simple simulated gasification atmosphere at elevated temperature. Because the electron-beam coating instrument suffered irreparable breakdown, several alternative methods were tested in an effort to produce a nitrogen-impermeable, hydrogen-permeable membrane on porous sintered steel substrates. None of the preparation methods proved successful in sealing the porous substrate against nitrogen gas. To provide a nitrogen-impermeable ZnS material to test for hydrogen permeability, two ZnS infrared sample windows were purchased. These relatively thick ''membranes'' did not show measurable permeation of hydrogen, either due to lack of absorption or a negligible permeation rate due to their thickness. To determine if hydrogen was indeed adsorbed, thermogravimetric and differential thermal analyses tests were performed on samples of ZnS powder. A significant uptake of hydrogen gas occurred, corresponding to a maximum of 1 mole H{sub 2} per 1 mole ZnS at a temperature of 175 C. The hydrogen remained in the material at ambient temperature in a hydrogen atmosphere, but approximately 50% would be removed in argon. Reheating in a hydrogen atmosphere resulted in no additional hydrogen uptake. Differential scanning calorimetry indicated that the hydrogen uptake was probably due to the formation of a zinc-sulfur-hydrogen species resulting in the formation of hydrogen sulfide. The zinc sulfide was found to be unstable above approximately 200 C, probably with the reduction to metallic zinc with the evolution of hydrogen sulfide. The work has shown that ZnS is not a viable candidate for a high-temperature hydrogen separation membrane.

  4. Application of Proton Conductors to Hydrogen Monitoring for Liquid Metal and Molten Salt Systems

    NASA Astrophysics Data System (ADS)

    Kondo, Masatoshi; Muroga, Takeo; Katahira, Koji; Oshima, Tomoko

    The chemical control of impurity such as hydrogen and oxygen in coolants is one of the critical issues for the development of liquid metal cooled fast reactors and self-cooled liquid breeder blankets for fusion reactors. Especially, hydrogen (isotopes) level is the key parameter for corrosion and mechanical properties of the in-reactor components. For fission reactors, the monitor of hydrogen level in the melt is important for safety operation. The control of tritium is essential for the tritium breeding performance of the fusion reactors. Therefore, on-line hydrogen sensing is a key technology for these systems. In the present study, conceptual design for the on-line hydrogen sensor to be used in liquid sodium (Na), lead (Pb), lead-bismuth (Pb-Bi), lithium (Li), lead-lithium (Pb-17Li) and molten salt LiF-BeF2 (Flibe) was performed. The cell of hydrogen sensor is made of a solid electrolyte. The solid electrolyte proposed in this study is the CaZrO3-based ceramics, which is well-known as proton conducting ceramics. In this concept, the cell is immersed into the melt which is containing the hydrogen at the activity of PH1 of ambient atmosphere. Then, the cell is filled with Ar-H2 mixture gas at regulated hydrogen activity of PH2. The electromotive force (EMF) is obtained by the proton conduction in the electro chemical system expressed as Pt, Melt(PH1) | Proton conductor | PH2, Pt. The Nernst equation is used for the evaluation of the hydrogen activity from the obtained EMF. The evaluations of expected performance of the sensor in liquid Na, Pb, Pb-Bi, Pb-17Li, Li and Flibe were carried out by means of the measurement test in gas atmosphere at hydrogen activities equivalent to those for the melts in the reactor conditions. In the test, the hydrogen activity in the gas varied from 2.2x10-14 to 1. The sensor exhibited good response, stability and reproducibility.

  5. Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

    NASA Technical Reports Server (NTRS)

    Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

    1993-01-01

    Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

  6. Getter trap for removing hydrogen and oxygen from a liquid metal

    SciTech Connect

    Grundy, B.R

    1989-05-16

    A liquid metal cooled nuclear reactor system is described comprising: a primary coolant loop including a primary liquid metal coolant, a liquid metal nuclear reactor and a first heat exchanger; a secondary coolant loop including a secondary liquid metal coolant, and first heat exchanger and a second heat exchanger; a third coolant loop including a water coolant, the second heat exchanger and a steam driven device wherein heat from the secondary liquid metal coolant of the secondary liquid metal coolant loop is transferred to the water coolant through the second heat exchanger, and the water coolant flow through the second heat exchanger, the steam driven device and back to the second heat exchanger; a getter trap, disposed in at least one of the primary and the secondary coolant loops, being capable of removing hydrogen and oxygen from the liquid metal flowing in the loops and comprising: an elongated, closed housing having an inlet at one end thereof and an outlet at the other end; a getter material randomly disposed within the housing, the getter material comprising a zirconium-containing substrate of hollow, tubular sections having a coating thereon of a gettering alloy of zirconium, vanadium, and iron.

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

    SciTech Connect

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

    2010-01-29

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen generation by no more than a factor of three while disodium phosphate increased the corrosion and hydrogen generation rates slightly. U(VI) showed some promise in attenuating hydrogen but only initial testing was completed. Uranium metal corrosion rates also were measured. Under many conditions showing high hydrogen gas attenuation, uranium metal continued to corrode at rates approaching those observed without additives. This combination of high hydrogen attenuation with relatively unabated uranium metal corrosion is significant as it provides a means to eliminate uranium metal by its corrosion in water without the accompanying hazards otherwise presented by hydrogen generation.

  8. Curvature and ionization-induced reversible hydrogen storage in metalized hexagonal B36

    NASA Astrophysics Data System (ADS)

    Liu, Chun-Sheng; Wang, Xiangfu; Ye, Xiao-Juan; Yan, Xiaohong; Zeng, Zhi

    2014-11-01

    The synthesis of quasiplanar boron clusters (B36) with a central hexagonal hole provides the first experimental evidence that a single-atomic-layer borophene with hexagonal vacancies is potentially viable [Z. Piazza, H. Hu, W. Li, Y. Zhao, J. Li, and L. S. Wang, Nat. Commun. 5, 3113 (2014)]. However, owing to the hexagonal holes, tunning the electronic and physical properties of B36 through chemical modifications is not fully understood. Based on (van der Waals corrected-) density functional theory, we show that Li adsorbed on B36 and B^-_{36} clusters can serve as reversible hydrogen storage media. The present results indicate that the curvature and ionization of substrates can enhance the bond strength of Li due to the energetically favorable B 2p-Li 2p orbitals hybridization. Both the polarization mechanism and the orbital hybridization between H-s orbitals and Li-2s2p orbitals contribute to the adsorption of H2 molecules and the resulting adsorption energy lies between the physisorbed and chemisorbed states. Interestingly, the number of H2 in the hydrogen storage medium can be measured by the appearance of the negative differential resistance behavior at different bias voltage regions. Furthermore, the cluster-assembled hydrogen storage materials constructed by metalized B36 clusters do not cause a decrease in the number of adsorbed hydrogen molecules per Li. The system reported here is favorable for the reversible hydrogen adsorption/desorption at ambient conditions.

  9. Curvature and ionization-induced reversible hydrogen storage in metalized hexagonal B36.

    PubMed

    Liu, Chun-Sheng; Wang, Xiangfu; Ye, Xiao-Juan; Yan, Xiaohong; Zeng, Zhi

    2014-11-21

    The synthesis of quasiplanar boron clusters (B36) with a central hexagonal hole provides the first experimental evidence that a single-atomic-layer borophene with hexagonal vacancies is potentially viable [Z. Piazza, H. Hu, W. Li, Y. Zhao, J. Li, and L. S. Wang, Nat. Commun. 5, 3113 (2014)]. However, owing to the hexagonal holes, tunning the electronic and physical properties of B36 through chemical modifications is not fully understood. Based on (van der Waals corrected-) density functional theory, we show that Li adsorbed on B36 and B36 (-) clusters can serve as reversible hydrogen storage media. The present results indicate that the curvature and ionization of substrates can enhance the bond strength of Li due to the energetically favorable B 2p-Li 2p orbitals hybridization. Both the polarization mechanism and the orbital hybridization between H-s orbitals and Li-2s2p orbitals contribute to the adsorption of H2 molecules and the resulting adsorption energy lies between the physisorbed and chemisorbed states. Interestingly, the number of H2 in the hydrogen storage medium can be measured by the appearance of the negative differential resistance behavior at different bias voltage regions. Furthermore, the cluster-assembled hydrogen storage materials constructed by metalized B36 clusters do not cause a decrease in the number of adsorbed hydrogen molecules per Li. The system reported here is favorable for the reversible hydrogen adsorption/desorption at ambient conditions. PMID:25416890

  10. High performance hydrogen storage from Be-BTB metal-organic framework at room temperature.

    PubMed

    Lim, Wei-Xian; Thornton, Aaron W; Hill, Anita J; Cox, Barry J; Hill, James M; Hill, Matthew R

    2013-07-01

    The metal-organic framework beryllium benzene tribenzoate (Be-BTB) has recently been reported to have one of the highest gravimetric hydrogen uptakes at room temperature. Storage at room temperature is one of the key requirements for the practical viability of hydrogen-powered vehicles. Be-BTB has an exceptional 298 K storage capacity of 2.3 wt % hydrogen. This result is surprising given that the low adsorption enthalpy of 5.5 kJ mol(-1). In this work, a combination of atomistic simulation and continuum modeling reveals that the beryllium rings contribute strongly to the hydrogen interaction with the framework. These simulations are extended with a thermodynamic energy optimization (TEO) model to compare the performance of Be-BTB to a compressed H2 tank and benchmark materials MOF-5 and MOF-177 in a MOF-based fuel cell. Our investigation shows that none of the MOF-filled tanks satisfy the United States Department of Energy (DOE) storage targets within the required operating temperatures and pressures. However, the Be-BTB tank delivers the most energy per volume and mass compared to the other material-based storage tanks. The pore size and the framework mass are shown to be contributing factors responsible for the superior room temperature hydrogen adsorption of Be-BTB. PMID:23805913

  11. Mn in misch-metal based superlattice metal hydride alloy - Part 1 structural, hydrogen storage and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Young, K.; Wong, D. F.; Wang, L.; Nei, J.; Ouchi, T.; Yasuoka, S.

    2015-03-01

    The structural, gaseous phase hydrogen storage, and electrochemical properties of a series of Mn-modified misch-metal based superlattice metal hydride alloys were investigated in part one of this two-part series of papers. X-ray diffraction analysis showed that these alloys are all multi-phased compositions with different abundances of AB2, AB3, A2B7, AB4, and AB5 phases. Substitution of Ni in the B-site by Mn promotes AB5 phase formation and decreases both gaseous phase and electrochemical capacities due to the reduction in the abundance of main hexagonal A2B7 phase. AC impedance and magnetic susceptibility measurement were employed to characterize the surface of Mn-free and Mn-modified alloys and show deterioration in surface catalytic ability as the Mn-content increases. Mn-modification adversely affected misch-metal based superlattice metal hydride alloy properties such as phase homogeneity, capacity, cycle stability, high-rate performance, and surface reaction.

  12. Micro-machined thin film hydrogen gas sensor, and method of making and using the same

    NASA Technical Reports Server (NTRS)

    DiMeo, Jr., Frank (Inventor); Bhandari, Gautam (Inventor)

    2001-01-01

    A hydrogen sensor including a thin film sensor element formed, e.g., by metalorganic chemical vapor deposition (MOCVD) or physical vapor deposition (PVD), on a microhotplate structure. The thin film sensor element includes a film of a hydrogen-interactive metal film that reversibly interacts with hydrogen to provide a correspondingly altered response characteristic, such as optical transmissivity, electrical conductance, electrical resistance, electrical capacitance, magnetoresistance, photoconductivity, etc., relative to the response characteristic of the film in the absence of hydrogen. The hydrogen-interactive metal film may be overcoated with a thin film hydrogen-permeable barrier layer to protect the hydrogen-interactive film from deleterious interaction with non-hydrogen species. The hydrogen sensor of the invention may be usefully employed for the detection of hydrogen in an environment susceptible to the incursion or generation of hydrogen and may be conveniently configured as a hand-held apparatus.

  13. Alkali-Metal-Ion-Assisted Hydrogen Atom Transfer in the Homocysteine Radical.

    PubMed

    Lesslie, Michael; Lau, Justin Kai-Chi; Lawler, John T; Siu, K W Michael; Oomens, Jos; Berden, Giel; Hopkinson, Alan C; Ryzhov, Victor

    2016-02-01

    Intramolecular hydrogen atom transfer (HAT) was examined in homocysteine (Hcy) thiyl radical/alkali metal ion complexes in the gas phase by combination of experimental techniques (ion-molecule reactions and infrared multiple photon dissociation spectroscopy) and theoretical calculations. The experimental results unequivocally show that metal ion complexation (as opposed to protonation) of the regiospecifically generated Hcy thiyl radical promotes its rapid isomerisation into an α-carbon radical via HAT. Theoretical calculations were employed to calculate the most probable HAT pathway and found that in alkali metal ion complexes the activation barrier is significantly lower, in full agreement with the experimental data. This is, to our knowledge, the first example of a gas-phase thiyl radical thermal rearrangement into an α-carbon species within the same amino acid residue and is consistent with the solution phase behaviour of Hcy radical. PMID:26836574

  14. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production

    NASA Astrophysics Data System (ADS)

    Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen (David)

    2015-03-01

    Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts.

  15. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production

    PubMed Central

    Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen (David)

    2015-01-01

    Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts. PMID:25758159

  16. Metal-and hydrogen-bonding competition during water absorption on Pd(111) and Ru(0001)

    SciTech Connect

    Tatarkhanov, Mouslim; Ogletree, D. Frank; Rose, Franck; Mitsui, Toshiyuki; Fomin, Evgeny; Rose, Mark; Cerda, Jorge I.; Salmeron, Miquel

    2009-09-03

    The initial stages of water adsorption on the Pd(111) and Ru(0001) surfaces have been investigated experimentally by Scanning Tunneling Microscopy in the temperature range between 40 K and 130 K, and theoretically with Density Functional Theory (DFT) total energy calculations and STM image simulations. Below 125 K water dissociation does not occur at any appreciable rate and only molecular films are formed. Film growth starts by the formation of flat hexamer clusters where the molecules bind to the metal substrate through the O-lone pair while making H-bonds with neighboring molecules. As coverage increases, larger networks of linked hexagons are formed with a honeycomb structure, which requires a fraction of the water molecules to have their molecular plane perpendicular to the metal surface with reduced water-metal interaction. Energy minimization favors the growth of networks with limited width. As additional water molecules adsorb on the surface they attach to the periphery of existing islands, where they interact only weakly with the metal substrate. These molecules hop along the periphery of the clusters at intermediate temperatures. At higher temperatures they bind to the metal to continue the honeycomb growth. The water-Ru interaction is significantly stronger than the water-Pd interaction, which is consistent with the greater degree of hydrogen-bonded network formation and reduced water-metal bonding observed on Pd relative to Ru.

  17. Hydrogen physisorption on metal-organic framework linkers and metalated linkers: a computational study of the factors that control binding strength.

    PubMed

    Tsivion, Ehud; Long, Jeffrey R; Head-Gordon, Martin

    2014-12-24

    In order for hydrogen gas to be used as a fuel, it must be stored in sufficient quantity on board the vehicle. Efforts are being made to increase the hydrogen storage capabilities of metal-organic frameworks (MOFs) by introducing unsaturated metal sites into their linking element(s), as hydrogen adsorption centers. In order to devise successful hydrogen storage strategies there is a need for a fundamental understanding of the weak and elusive hydrogen physisorption interaction. Here we report our findings from the investigation of the weak intermolecular interactions of adsorbed hydrogen molecules on MOF-linkers by using cluster models. Since physical interactions such as dispersion and polarization have a major contribution to attraction energy, our approach is to analyze the adsorption interaction using energy decomposition analysis (EDA) that distinguishes the contribution of the physical interactions from the charge-transfer (CT) "chemical" interaction. Surprisingly, it is found that CT from the adsorbent to the ?*(H2) orbital is present in all studied complexes and can contribute up to approximately -2 kJ/mol to the interaction. When metal ions are present, donation from the ?(H2) ? metal Rydberg-like orbital, along with the adsorbent ? ?*(H2) contribution, can contribute from -2 to -10 kJ/mol, depending on the coordination mode. To reach a sufficient adsorption enthalpy for practical usage, the hydrogen molecule must be substantially polarized. Ultimately, the ability of the metalated linker to polarize the hydrogen molecule is highly dependent on the geometry of the metal ion coordination site where a strong electrostatic dipole or quadrupole moment is required. PMID:25415078

  18. Develop improved metal hydride technology for the storage of hydrogen. Final technical report

    SciTech Connect

    Sapru, K.

    1998-12-04

    The overall objective was to develop commercially viable metal hydrides capable of reversibly storing at least 3 wt.% hydrogen for use with PEM fuel cells and hydrogen fueled internal combustion engine (HICE) applications. Such alloys are expected to result in system capacities of greater than 2 wt.%, making metal hydride storage systems (MHSS`s) a practical means of supplying hydrogen for many consumer applications. ECD`s (Energy Conversion Devices, Inc.) past work on sputtered thin films of transition metal-based alloys led to the commercialization of it`s nickel/metal hydride batteries, and similar work on thin film Mg-based alloys demonstrated potential to achieve very high gravimetric and volumetric energy densities approaching 2,500 Wh/Kg and 2,500 Wh/M{sup 3} respectively. Under this 2-year cost shared project with the DOE, the authors have successfully demonstrated the feasibility of scaling up the Mg-based hydrides from thin film to bulk production without substantial loss of storage capacity. ECD made progress in alloy development by means of compositional and process modification. Processes used include Mechanical Alloying, Melt spinning and novel Gas Phase Condensation. It was showed that the same composition when prepared by melt-spinning resulted in a more homogeneous material having a higher PCT plateau pressure as compared to mechanical alloying. It was also shown that mechanically alloyed Mg-Al-Zn results in much higher plateau pressures, which is an important step towards reducing the desorption temperature. While significant progress has been made during the past two years in alloy development and understanding the relationship between composition, structure, morphology, and processing parameters, additional R and D needs to be performed to achieve the goals of this work.

  19. Hydrogen purifier module and method for forming the same

    DOEpatents

    DeVries, Peter David (Spokane, WA)

    2012-02-07

    A hydrogen purifier utilizing a hydrogen permeable membrane, and a gas-tight seal, where the seal is uses a low temperature melting point metal, which upon heating above the melting point subsequently forms a seal alloy with adjacent metals, where the alloy has a melting point above the operational temperature of the purifier. The purifier further is constructed such that a degree of isolation exists between the metal that melts to form the seal and the active area of the purifier membrane, so that the active area of the purifier membrane is not corrupted. A method of forming a hydrogen purifier utilizing a hydrogen permeable membrane with a seal of the same type is also disclosed.

  20. Heavy metal removal from MSWI fly ash by electrokinetic remediation coupled with a permeable activated charcoal reactive barrier.

    PubMed

    Huang, Tao; Li, Dongwei; Kexiang, Liu; Zhang, Yuewei

    2015-01-01

    This paper presents the investigations into the feasibility of the application of a remediation system that couples electrokinetic remediation (EKR) with the permeable reactive barrier (PRB) concept for municipal solid waste incineration (MSWI) fly ash with activated charcoal as the PRB material. The experimental results of this study showed that the proposed combined method can effectively improve the remediation efficiency and that the addition of the oxalic acid to the PRB media before the coupled system can further enhance the remediation process. In the optimization tests, the maximum removals of Zn, Pb, Cu and Cd were achieved under different experimental conditions. The voltage gradient and processing time were shown to have significant effects on the removal of Cu and Cd, whereas the addition of the oxalic acid had a more significant influence on the removal of Pb. Generally, the processing time is the most significant factor in changing the removal rates of HMs in the enhanced coupled system. In terms of the leaching toxicity, the specimen remediated by ENEKR?+?PRB showed the lowest leaching value for each HM in the S2 and S3 regions. PMID:26486449

  1. Heavy metal removal from MSWI fly ash by electrokinetic remediation coupled with a permeable activated charcoal reactive barrier

    PubMed Central

    Huang, Tao; Li, Dongwei; Kexiang, Liu; Zhang, Yuewei

    2015-01-01

    This paper presents the investigations into the feasibility of the application of a remediation system that couples electrokinetic remediation (EKR) with the permeable reactive barrier (PRB) concept for municipal solid waste incineration (MSWI) fly ash with activated charcoal as the PRB material. The experimental results of this study showed that the proposed combined method can effectively improve the remediation efficiency and that the addition of the oxalic acid to the PRB media before the coupled system can further enhance the remediation process. In the optimization tests, the maximum removals of Zn, Pb, Cu and Cd were achieved under different experimental conditions. The voltage gradient and processing time were shown to have significant effects on the removal of Cu and Cd, whereas the addition of the oxalic acid had a more significant influence on the removal of Pb. Generally, the processing time is the most significant factor in changing the removal rates of HMs in the enhanced coupled system. In terms of the leaching toxicity, the specimen remediated by ENEKR + PRB showed the lowest leaching value for each HM in the S2 and S3 regions. PMID:26486449

  2. Heavy metal removal from MSWI fly ash by electrokinetic remediation coupled with a permeable activated charcoal reactive barrier

    NASA Astrophysics Data System (ADS)

    Huang, Tao; Li, Dongwei; Kexiang, Liu; Zhang, Yuewei

    2015-10-01

    This paper presents the investigations into the feasibility of the application of a remediation system that couples electrokinetic remediation (EKR) with the permeable reactive barrier (PRB) concept for municipal solid waste incineration (MSWI) fly ash with activated charcoal as the PRB material. The experimental results of this study showed that the proposed combined method can effectively improve the remediation efficiency and that the addition of the oxalic acid to the PRB media before the coupled system can further enhance the remediation process. In the optimization tests, the maximum removals of Zn, Pb, Cu and Cd were achieved under different experimental conditions. The voltage gradient and processing time were shown to have significant effects on the removal of Cu and Cd, whereas the addition of the oxalic acid had a more significant influence on the removal of Pb. Generally, the processing time is the most significant factor in changing the removal rates of HMs in the enhanced coupled system. In terms of the leaching toxicity, the specimen remediated by ENEKR + PRB showed the lowest leaching value for each HM in the S2 and S3 regions.

  3. Y3+, La3+, and some bivalent metals inhibited the opening of the Tl+-induced permeability transition pore in Ca2+-loaded rat liver mitochondria.

    PubMed

    Korotkov, Sergey; Konovalova, Svetlana; Emelyanova, Larisa; Brailovskaya, Irina

    2014-12-01

    We showed earlier that diminution of 2,4-dinitrophenol (DNP)-stimulated respiration and increase of both mitochondrial swelling and electrochemical potential (??mito) dissipation in medium containing TlNO3 and KNO3 were caused by opening of Tl(+)-induced mitochondrial permeability transition pore (MPTP) in the inner membrane of Ca(2+)-loaded rat liver mitochondria. The MPTP opening was studied in the presence of bivalent metal ions (Sr(2+), Ba(2+), Mn(2+), Co(2+) and Ni(2+)), trivalent metal ions (Y(3+) and La(3+)), and ruthenium red. We found that these metal ions (except Ba(2+) and Co(2+)) as well as ruthenium red inhibited to the MPTP opening that manifested in preventing both diminution of the DNP-stimulated respiration and increase of the swelling and of the ??mito dissipation in medium containing TlNO3, KNO3, and Ca(2+). Inhibition of the MPTP opening by Sr(2+) and Mn(2+) is suggested because of their interaction with high affinity Ca(2+) sites, facing the matrix side and participating in the MPTP opening. The inhibitory effects of metal ions (Y(3+), La(3+), and Ni(2+)), and ruthenium red are accordingly discussed in regard to competitive and noncompetitive inhibition of the mitochondrial Ca(2+)-uniporter. High concentrations (50?M) of Y(3+) and La(3+) favored of MPTP opening in the inner membrane of rat liver mitochondria in Ca(2+) free medium containing TlNO3. The latter MPTP opening was markedly eliminated by MPTP inhibitors (cyclosporine A and ADP). PMID:25172992

  4. The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors.

    PubMed

    Smith, Dan A; Beweries, Torsten; Blasius, Clemens; Jasim, Naseralla; Nazir, Ruqia; Nazir, Sadia; Robertson, Craig C; Whitwood, Adrian C; Hunter, Christopher A; Brammer, Lee; Perutz, Robin N

    2015-09-16

    The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability ? (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (-23.5 0.3 kJ mol(-1)) interlocks our study with Laurence's scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of p?-d? bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis. PMID:26302048

  5. Percolative metal-organic framework/carbon composites for hydrogen storage

    NASA Astrophysics Data System (ADS)

    Xie, Shuqian; Hwang, Jiann-Yang; Sun, Xiang; Shi, Shangzhao; Zhang, Zheng; Peng, Zhiwei; Zhai, Yuchun

    2014-05-01

    Percolative Metal-organic framework/Carbon (MOFAC) composites are synthesized by IRMOF8 (isoreticular metal-organic frameworks) directly depositing on activated carbon via heterogeneous nucleation. Carbon content is calculated by TGA (Thermogravimetric analysis) tests. XRD (X-ray diffraction) and FESEM (Field emission-scanning electron microscope) are carried out to characterize the structures of the samples. BET surface areas and the pore size distribution are measured. The dielectric constant is measured with impedance analyzer and a specially designed sample holder. The dielectric constants of the MOFAC composites rise with increasing the carbon content, and the composites possess the insulator-conductor transition as the carbon content increases from 17.77 wt% to 22.2 wt%. The composites are further tested for hydrogen storage capability under assist of the PMN-PT (single crystal lead magnesium niobate-lead titanate) generated electric field. With help from the PMN-PT, the hydrogen uptake capability is increased about 31.5% over the MOFAC3 (MOF-Carbon composite with 22.2 wt% of carbon) without PMN-PT, which is elucidated by the charge distribution mechanisms. The improved storage is due to a stronger electrostatic interaction between IRMOF8 and hydrogen molecule caused by field polarization. Meanwhile, rapid adsorption/desorption kinetics and total reversibility on the samples are observed in the present or absence of external electric field.

  6. SOLUBILITY OF IRON IN METALLIC HYDROGEN AND STABILITY OF DENSE CORES IN GIANT PLANETS

    SciTech Connect

    Wahl, Sean M.; Wilson, Hugh F.; Militzer, Burkhard

    2013-08-20

    The formation of the giant planets in our solar system, and likely a majority of giant exoplanets, is most commonly explained by the accretion of nebular hydrogen and helium onto a large core of terrestrial-like composition. The fate of this core has important consequences for the evolution of the interior structure of the planet. It has recently been shown that H{sub 2}O, MgO, and SiO{sub 2} dissolve in liquid metallic hydrogen at high temperature and pressure. In this study, we perform ab initio calculations to study the solubility of an innermost metallic core. We find dissolution of iron to be strongly favored above 2000 K over the entire pressure range (0.4-4 TPa) considered. We compare with and summarize the results for solubilities on other probable core constituents. The calculations imply that giant planet cores are in thermodynamic disequilibrium with surrounding layers, promoting erosion and redistribution of heavy elements. Differences in solubility behavior between iron and rock may influence evolution of interiors, particularly for Saturn-mass planets. Understanding the distribution of iron and other heavy elements in gas giants may be relevant in understanding mass-radius relationships, as well as deviations in transport properties from pure hydrogen-helium mixtures.

  7. Degradation of metallic surfaces under space conditions, with particular emphasis on Hydrogen recombination processes

    NASA Astrophysics Data System (ADS)

    Sznajder, Maciej; Geppert, Ulrich; Dudek, Mirosław

    2015-07-01

    The widespread use of metallic structures in space technology brings risk of degradation which occurs under space conditions. New types of materials dedicated for space applications, that have been developed in the last decade, are in majority not well tested for different space mission scenarios. Very little is known how material degradation may affect the stability and functionality of space vehicles and devices during long term space missions. Our aim is to predict how the solar wind and electromagnetic radiation degrade metallic structures. Therefore both experimental and theoretical studies of material degradation under space conditions have been performed. The studies are accomplished at German Aerospace Center (DLR) in Bremen (Germany) and University of Zielona Góra (Poland). The paper presents the results of the theoretical part of those studies. It is proposed that metal bubbles filled with Hydrogen molecular gas, resulting from recombination of the metal free electrons and the solar protons, are formed on the irradiated surfaces. A thermodynamic model of bubble formation has been developed. We study the creation process of H2 -bubbles as function of, inter alia, the metal temperature, proton dose and energy. Our model has been verified by irradiation experiments completed at the DLR facility in Bremen. Consequences of the bubble formation are changes of the physical and thermo-optical properties of such degraded metals. We show that a high surface density of bubbles (up to 108cm-2) with a typical bubble diameter of ∼ 0.4 μm will cause a significant increase of the metallic surface roughness. This may have serious consequences to any space mission. Changes in the thermo-optical properties of metallic foils are especially important for the solar sail propulsion technology because its efficiency depends on the effective momentum transfer from the solar photons onto the sail structure. This transfer is proportional to the reflectivity of a sail. Therefore, the propulsion abilities of sail material will be affected by the growing population of the molecular Hydrogen bubbles on metallic foil surfaces.

  8. Tunable hydrogen storage in magnesium-transition metal compounds: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Er, Sleyman; Tiwari, Dhirendra; de Wijs, Gilles A.; Brocks, Geert

    2009-01-01

    Magnesium dihydride (MgH2) stores 7.7wt% hydrogen but it suffers from a high thermodynamic stability and slow (de)hydrogenation kinetics. Alloying Mg with lightweight transition metals (TM) (=Sc,Ti,V,Cr) aims at improving the thermodynamic and kinetic properties. We study the structure and stability of MgxTM1-xH2 compounds, x=[0-1] , by first-principles calculations at the level of density functional theory. We find that the experimentally observed sharp decrease in hydrogenation rates for x?0.8 correlates with a phase transition of MgxTM1-xH2 from a fluorite to a rutile phase. The stability of these compounds decreases along the series Sc, Ti, V, and Cr. Varying the TM and the composition x , the formation enthalpy of MgxTM1-xH2 can be tuned over the substantial range of 0-2 eV/f.u. Assuming however that the alloy MgxTM1-x does not decompose upon dehydrogenation, the enthalpy associated with reversible hydrogenation of compounds with a high magnesium content (x=0.75) is close to that of pure Mg.

  9. OPTIMIZATION OF INTERNAL HEAT EXCHANGERS FOR HYDROGEN STORAGE TANKS UTILIZING METAL HYDRIDES

    SciTech Connect

    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.

  10. A permeable reactive barrier (PRB) media sequence for the remediation of heavy metal and hydrocarbon contaminated water: A field assessment at Casey Station, Antarctica.

    PubMed

    Statham, Tom M; Stark, Scott C; Snape, Ian; Stevens, Geoffrey W; Mumford, Kathryn A

    2016-03-01

    A field trial was conducted at Casey Station, Antarctica to assess the suitability of a permeable reactive barrier (PRB) media sequence for the remediation of sites containing both hydrocarbon and heavy metal contamination. An existing PRB was modified to assess a sequence consisting of three sections: (i) Nutrient release/hydrocarbon sorption using ZeoPro™ and granular activated carbon; (ii) Phosphorus and heavy metal capture by granular iron and sand; (iii) Nutrient and excess iron capture by zeolite. The media sequence achieved a greater phosphorus removal capacity than previous Antarctic PRB configurations installed on site. Phosphorus concentrations were reduced during flow through the iron/sand section and iron concentrations were reduced within the zeolite section. However, non-ideal flow was detected during a tracer test and supported by analysis of media and liquid samples from the second summer of operation. Results indicate that the PRB media sequence trialled might be appropriate for other locations, especially less environmentally challenging contaminated sites. PMID:26774301

  11. Compact hydrogenator

    NASA Technical Reports Server (NTRS)

    Simmonds, P. G. (Inventor)

    1974-01-01

    The development and characteristics of a hydrogenating apparatus are described. The device consists of a reaction chamber which is selectively permeable to atomic hydrogen and catalytically active to a hydrogenating reaction. In one device, hydrogen is pumped out of the reaction chamber while the reactant remains inside to remove molecular hydrogen so that more atomic hydrogen can pass through the walls. In another device, the reactant is pumped through the reaction chamber, and the hydrogen is removed from the material leaving the chamber. The reactant is then cycled through the chamber.

  12. Hydrogen cracking in the heat affected zone of high strength steels - year 2, development of weld metal test

    SciTech Connect

    Graville, B.A.

    1997-03-01

    In previous work the notched bend test had been developed for evaluating the sensitivity of the heat affected zone (HAZ) of a weld to hydrogen cracking. In the present work the test was modified to allow the evaluation of weld metal. The test specimen uses a Charpy-V notch placed in the weld metal after welding and prior to loading in three point bending. The deflection to first load drop is used as the measure of sensitivity to cracking. The results showed that weld metal could readily be evaluated with the test discriminating among weld metals of different composition and hydrogen content. Finite element analysis was undertaken and showed that for the two weld metals tested, cracking occurred at the same local stress when the hydrogen content was the same despite differences in strength. A finite difference model was used to calculate the distribution of hydrogen as a function of aging time. Although the general trends were confirmed by the experimental measurements of hydrogen content, there was considerable scatter attributed to the small hydrogen volumes measured.

  13. Roles of metal ion complexation and membrane permeability in the metal flux through lipophilic membranes. Labile complexes at permeation liquid membranes.

    PubMed

    Zhang, Zeshi; Buffle, Jacques; van Leeuwen, Herman P; Wojciechowski, Kamil

    2006-08-15

    The various physicochemical factors that influence the flux of carrier-transported metal ions through permeation liquid membranes (PLM) are studied systematically. Understanding PLM behavior is important (i) to optimize the application of PLM as metal speciation sensors in environmental media and (ii) because PLM may serve as bioanalogical devices that help to elucidate the environmental physicochemical processes occurring at the surface of biological membranes. Diffusion of free and complexed metal ions in solution, as well as diffusion of the metal carrier complex in the membrane, is considered. The respective roles of diffusion layer thickness, ligand concentration, complex stability, carrier concentration, and membrane thickness are studied experimentally in detail and compared with theory, using various labile complexes, namely, Pb(II)-diglycolate, Cu(II)-diglycolate, and Cu(II)-N-(2-carboxyphenyl)glycine. Conditions where either membrane diffusion or solution diffusion is rate limiting are clearly discriminated. It is shown in particular, that, by tuning the carrier concentration or membrane thickness, either the free metal ion concentration or the total labile metal species are measured. PLM can thus be used to determine whether models based on the free ion activity in solution (such as BLM or FIAM models) are applicable to metal uptake by microorganisms in a real natural medium. PMID:16906713

  14. Uranium metal reactions with hydrogen and water vapour and the reactivity of the uranium hydride produced

    SciTech Connect

    Godfrey, H.; Broan, C.; Goddard, D.; Hodge, N.; Woodhouse, G.; Diggle, A.; Orr, R.

    2013-07-01

    Within the nuclear industry, metallic uranium has been used as a fuel. If this metal is stored in a hydrogen rich environment then the uranium metal can react with the hydrogen to form uranium hydride which can be pyrophoric when exposed to air. The UK National Nuclear Laboratory has been carrying out a programme of research for Sellafield Limited to investigate the conditions required for the formation and persistence of uranium hydride and the reactivity of the material formed. The experimental results presented here have described new results characterising uranium hydride formed from bulk uranium at 50 and 160 C. degrees and measurements of the hydrolysis kinetics of these materials in liquid water. It has been shown that there is an increase in the proportion of alpha-uranium hydride in material formed at lower temperatures and that there is an increase in the rate of reaction with water of uranium hydride formed at lower temperatures. This may at least in part be attributable to a difference in the reaction rate between alpha and beta-uranium hydride. A striking observation is the strong dependence of the hydrolysis reaction rate on the temperature of preparation of the uranium hydride. For example, the reaction rate of uranium hydride prepared at 50 C. degrees was over ten times higher than that prepared at 160 C. degrees at 20% extent of reaction. The decrease in reaction rate with the extent of reaction also depended on the temperature of uranium hydride preparation.

  15. Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

    2015-08-01

    Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt-nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt-N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s-1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols.

  16. Surface plasmon resonance hydrogen sensor based on metallic grating with high sensitivity.

    PubMed

    Lin, Kaiqun; Lu, Yonghua; Chen, Junxue; Zheng, Rongsheng; Wang, Pei; Ming, Hai

    2008-11-10

    High sensitivity is obtained at larger resonant incident angle if negative diffraction order of metallic grating is used to excite the surface plasmon. A highly sensitive grating-based surface plasmon resonance (SPR) sensor is designed for the hydrogen detection. A thin palladium (Pd) film deposited on the grating surface is used as transducer. The influences of grating period and the thickness of Pd on the performance of sensor are investigated using rigorous coupled-wave analysis (RCWA) method. The sensitivity as well as the width of the SPR curves and reflective amplitude is considered simultaneously for designing the grating-based SPR hydrogen sensor, and a set of optimized structural parameters is presented. The performance of grating-based SPR sensor is also compared with that of conventional prism-based SPR sensor. PMID:19581945

  17. Performance of a metal hydride store on the "Ross Barlow" hydrogen powered canal boat.

    PubMed

    Bevan, A I; Zttel, A; Book, D; Harris, I R

    2011-01-01

    This project involved the conversion of a British Waterways maintenance craft to a canal boat, powered by a combination of a solid-state hydrogen store, Proton Exchange Membrane (PEM) fuel cell, lead-acid battery pack and a high-efficiency, permanent magnet (NdFeB) electric motor. These replaced the conventional diesel engine thus eliminating water, noise, local and general atmospheric pollution. The "Protium" project applies modern technologies to a traditional mode of transportation. The TiMn2-based metal hydride store exhibited excellent performance as an effective means of storing 4 kg of hydrogen with a suitable desorption flow rate and temperature adequate for the operation of a 1 kW PEM fuel cell in a water-based environment. PMID:22455080

  18. A high-efficiency power cycle in which hydrogen is compressed by absorption in metal hydrides.

    PubMed

    Powell, J R; Salzano, F J; Yu, W S; Milau, J S

    1976-07-23

    A high-efficiency power cycle is proposed in which molecular hydrogen gas is used as a working fluid in a regenerative closed Brayton cycle. The hydrogen gas is compressed by an absorption-desorption cycle on metal hydride (FeTiH(x)) beds. Low-temperature solar or geothermal heat (temperature about 100 degrees C) is used for the compression process, and high-temperature fossil fuel or nuclear heat (temperature about 700 degrees C) supplies the expansion work in the turbine. Typically, about 90 percent of the high-temperature heat input is converted to electricity, while about 3 kilowatts of low-temperature heat is required per kilowatt of electrical output. PMID:17745726

  19. Hydrogen effects on the mechanical and fracture behavior of Zr-Ti-Ni-Cu-Be bulk metallic glass

    SciTech Connect

    Suh, D.; Dauskardt, R.H.

    2000-01-01

    Recently developed Zr-Ti-Ni-Cu-Be bulk metallic glasses have considerable potential for use in a variety of advanced engineering applications due to their extraordinarily high strength, moderate toughness and high strength-to-weight ratio. Active research is under way to elucidate the fundamental flow, fracture and subcritical crack-growth behavior of bulk metallic glasses using conventional fracture mechanics methodologies made possible by their availability in bulk metallic glasses using conventional fracture mechanics methodologies made possible by their availability in bulk form. However, the influence of hydrogen on the mechanical and fracture behavior of the bulk metallic glasses and the fundamental nature of the interaction of hydrogen with the amorphous microstructure has received almost no attention. Accordingly, the objective of the present work is to investigate the effects of pre-charged hydrogen on the mechanical and fracture behavior of a Zr-Ti-Ni-Cu-Be bulk metallic glass, specifically hardness and crack-propagation behavior under both monotonic and cyclic loading. In addition, characterization of the metallic glass using high-resolution electron microscopy and X-ray diffraction together with differential scanning calorimetry was performed to assess the effect of hydrogen on the amorphous microstructure. It is found that whereas intrinsic toughness is degraded by pre-charged hydrogen, the apparent resistance to fatigue crack growth is improved. Such conflicting results are interpreted by a mutual competition between degradation of the material's inherent resistance to crack extension and a reduced crack driving force by various crack tip shielding mechanisms.

  20. Surface science and electrochemical studies of metal-modified carbides for fuel cells and hydrogen production

    NASA Astrophysics Data System (ADS)

    Kelly, Thomas Glenn

    Carbides of the early transition metals have emerged as low-cost catalysts that are active for a wide range of reactions. The surface chemistry of carbides can be altered by modifying the surface with small amounts of admetals. These metal-modified carbides can be effective replacements for Pt-based bimetallic systems, which suffer from the drawbacks of high cost and low thermal stability. In this dissertation, metal-modified carbides were studied for reactions with applications to renewable energy technologies. It is demonstrated that metal-modified carbides possess high activity for alcohol reforming and electrochemical hydrogen production. First, the surface chemistry of carbides towards alcohol decomposition is studied using density functional theory (DFT) and surface science experiments. The Vienna Ab initio Simulation Package (VASP) was used to calculate the binding energies of alcohols and decomposition intermediates on metal-modified carbides. The calculated binding energies were then correlated to reforming activity determined experimentally using temperature programmed desorption (TPD). In the case of methanol decomposition, it was found that tungsten monocarbide (WC) selectively cleaved the C-O bond to produce methane. Upon modifying the surface with a single layer of metal such as Ni, Pt, or Rh, the selectivity shifted towards scission of the C-H bonds while leaving the C-O bond intact, producing carbon monoxide (CO) and H2. High resolution energy loss spectroscopy (HREELS) was used to examine the bond breaking sequence as a function of temperature. From HREELS, it was shown that the surfaces followed an activity trend of Rh > Ni > Pt. The Au-modified WC surface possessed too low of a methanol binding energy, and molecular desorption of methanol was the most favorable pathway on this surface. Next, the ability of Rh-modified WC to break the C-C bond of C2 and C3 alcohols was demonstrated. HREELS showed that ethanol decomposed through an acetaldehyde intermediate on Rh/WC, and that the C-C bond was broken by 200 K. Finally, the suitability of metal-modified molybdenum carbide (Mo2C) as an ethanol decomposition catalyst was studied. A new reaction pathway of partial dehydrogenation to an acetaldehyde product was achieved by using Cu as an admetal. The second section of this dissertation was the study of metal-modified carbides for electrochemical hydrogen evolution. Previously, DFT calculations had predicted a similar hydrogen binding energy (HBE) between Pd-modified carbides and bulk Pd. Linear sweep voltammograms (LSV) demonstrated that Pd-modified WC and Mo2C possessed hydrogen evolution activity orders of magnitude greater than the bare carbides. The long-term stability of these surfaces under operating conditions was also examined. A two-hour chronopotentiometry experiment was performed, after which x-ray photoelectron spectroscopy (XPS) found that negligible loss of the Pd overlayer occurred. As an extension of this work, a DFT study was performed for several admetal/Mo2C combinations. It was shown that the HBE of these surfaces mostly correlated with the pure metal HBE. Some of these combinations were tested experimentally, but were unstable in the acidic electrolyte.

  1. Catalytic hydrogenation of carbon dioxide to formic acid by transition-metal complexes

    SciTech Connect

    Zhang, Junzhong; Li, Z.; Wang, H.; Wang, C.

    1993-12-31

    For the unfavorable effects of carbon dioxide on the environment and ecology and for the increasing scarcity of organic carbon carriers for the future, the study of conversion of CO{sub 2} into organic compounds is currently attracting widespread interest. The production of formic acid from the hydrogenation of carbon dioxide in alcohol by transition metals (Ru, Rh, Pd, Ir, Fe, Co, Ni) and their complexes as catalysts is reported. RuH{sub 2}(CO)(PPh{sub 3}){sub 3}, RhH(CO)(PPh{sub 3}){sub 3}, and IrH(CO)(PPh{sub 3}){sub 3}, have been found to be effective catalysts for the hydrogenation of CO{sub 2} in hydrogenation of CO{sub 2} in alcohol`s under mild conditions (loading pressures of CO{sub 2} and H{sub 2}, 2.5MPa each, and 333K) to provide formic acid. Ru and its complex RuH{sub 2}(CO)(Ph{sub 3}){sub 3} were shown to be most effective. Its activity reached at 40 mol HCOOH/mol cat-hr under conditions mention above. A catalytic cycle is proposed, which starts with formation of RuH{sub 2}(C)(PPh{sub 3}){sub 3} as the catalytic activity species, then CO{sub 2} insertion taking place to form metal-formate intermediate, and last releasing formic acid from metal center, either by reductive elimination of the hydrido formato ligands or ligand-assisted heterolytic splitting of dihydrogen with loss of formic acid.

  2. Anion Coordination in Metal-Organic Frameworks Functionalized with Urea Hydrogen-Bonding Groups

    SciTech Connect

    Custelcean, Radu; Moyer, Bruce A.; Bryantsev, Vyacheslav; Hay, Benjamin P.

    2005-12-15

    A series of metal-organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups have been designed, synthesized, and structurally analyzed by single crystal X-ray diffraction to evaluate the efficacy of anion binding within the structural constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal-organic frameworks when the tendency for urea???urea self-association is decreased by strengthening the intramolelcular CH???O hydrogen bonding of N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N?-bis(m-pyridyl)urea (BPU) and N,N?-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies to self-associate into hydrogen-bonded chains compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO4)2, ZnSO4, Cu(NO3)2, Cu(CF3SO3)2, AgNO3 and AgSO3CH3. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion binding by the urea functionalities was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate. This research was sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy, under contract number DE-AC05-00OR22725 with Oak Ridge National Laboratory (managed by UT-Battelle, LLC), and performed at Oak Ridge National laboratory and Pacific Northwest National Laboratory (managed by Battelle for the U.S. Department of Energy under contract DE-AC05-76RL01830). This research was performed in part using the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences laboratory, a national scientific user facility sponsored by the U.S. Department of Energy's Office of Biological and Environmental Research located at the Pacific Northwest National Laboratory.

  3. Theoretical analysis for the heterogeneous decomposition of hydrogen sulfide to hydrogen on an iron-metallic plate in a laminar stagnation-point flow

    NASA Astrophysics Data System (ADS)

    Martnez, J. C.; Mndez, F.; Trevio, C.

    2006-12-01

    In this work, we have theoretically analyzed the conversion process of hydrogen sulfide, H 2S, to atomic hydrogen, H 0, in a planar stagnation-point flow over an iron-metallic surface. We assume that a binary mixture of hydrogen sulfide and methane composes the laminar stagnation flow. In order to characterize this complex phenomenon with very specific chemical activities on the surface of the metallic plate, we propose a heterogeneous reaction scheme based on four reactions: two electrochemical, one adsorption and an additional exothermic reaction needed to complete the direct conversion of hydrogen sulfide to hydrogen on the surface of the iron. The nondimensional governing equations, which include the mass species and momentum conservation of the mixture and the molecular diffusion of hydrogen into the iron plate, are numerically solved by conventional finite-difference methods. The numerical results show the critical conditions of the H 2S decomposition as functions of the involved nondimensional parameters of the present model. In particular, we show parametrically the influence that has the initial concentration of H 2S on the surface coverage of the chemical products HS - H + and H 0 derived from the chemical and electrochemical reactions.

  4. Unusual hydrogen bonding behavior in binary complexes of coinage metal anions with water

    NASA Astrophysics Data System (ADS)

    Schneider, Holger; Boese, A. Daniel; Weber, J. Mathias

    2005-08-01

    We have studied the interaction of atomic coinage metal anions with water molecules by infrared photodissociation spectroscopy of M-H2OArn clusters (M =Cu, Ag, Au; n =1, 2). We compare our observations with calculations on density-functional and coupled cluster levels of theory. The gold anion is bound to the water molecule by a single ionic hydrogen bond, similar to the halide-water complexes. In contrast, zero-point motion in the silver and copper complexes leads to a deviation from this motif.

  5. Unusual hydrogen bonding behavior in binary complexes of coinage metal anions with water

    SciTech Connect

    Schneider, Holger; Boese, A. Daniel; Weber, J. Mathias

    2005-08-22

    We have studied the interaction of atomic coinage metal anions with water molecules by infrared photodissociation spectroscopy of M{sup -}{center_dot}H{sub 2}O{center_dot}Ar{sub n} clusters (M=Cu, Ag, Au; n=1, 2). We compare our observations with calculations on density-functional and coupled cluster levels of theory. The gold anion is bound to the water molecule by a single ionic hydrogen bond, similar to the halide-water complexes. In contrast, zero-point motion in the silver and copper complexes leads to a deviation from this motif.

  6. Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

    SciTech Connect

    Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J; Jensen, Craig M; Ozolins, Vidvuds; Siegel, Don

    2011-02-14

    UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. The assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 – LiAlH4 –Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the alanate from alkali hydride, Al and hydrogen, was hampering reversibility. The reverse reaction was then studied for the same phase diagram, starting with LiH, NaH, and MgH2, and Al. The study was extended to phase diagrams including KH and CaH2 as well. The observed hydrogen storage capacity in the Al hexahydrides was less than 4 wt. %, well short of DOE targets. The HT assay came on line and after certification with studies on NaAlH4, was first applied to the LiNH2 - LiBH4 - MgH2 phase diagram. The 60-point study elucidated trends within the system locating an optimum material of 0.6 LiNH2 – 0.3 MgH2 – 0.1 LiBH4 that stored about 4 wt. % H2 reversibly and operated below 220 °C. Also present was the phase Li4(NH2)3BH4, which had been discovered in the LiNH2 -LiBH4 system. This new ternary formulation performed much better than the well-known 2 LiNH2 – MgH2 system by 50 °C in the HT assay. The Li4(NH2)3BH4 is a low melting ionic liquid under our test conditions and facilitates the phase transformations required in the hydrogen storage reaction, which no longer relies on a higher energy solid state reaction pathway. Further study showed that the 0.6 LiNH2 – 0.3 MgH2 – 0.1 LiBH4 formulation was very stable with respect to ammonia and diborane desorption, the observed desorption was from hydrogen. This result could not have been anticipated and was made possible by the efficiency of HT combinatorial methods. Investigation of the analogous LiNH2 – LiBH4 – CaH2 phase diagram revealed new reversible hydrogen storage materials 0.625 LiBH4 + 0.375 CaH2 and 0.375 LiNH2 + 0.25 LiBH4 + 0.375 CaH2 operating at 1 wt. % reversible hydrogen below 175 °C. Powder x-ray diffraction revealed a new structure for the spent materials which had not been previously observed. While the storage capacity was not impressive, an important aspect is that it boron appears to participate in a low temperature reversible reaction. The last major area of study also focused on activating boron-based materials in order to exploit the tremendous gravimetric capacity of LiBH4. A number of LiNH2 – LiBH4 – transition metal (TM) systems were investigated for the following reasons. No additional leads were discovered in this system. Another major project activity was the assembly of a high throughput synthesis system. The automated synthesizer was set up in a glovebox and was capable of handling liquids and powders and carrying out sealed block syntheses up to 250 °C. Unfortunately, the synthesizer could not handle the delivery of the fine powders required fro hydrogen storage applications. Although the powder delivery system was overhauled and redesigned several times, this problem was never remedied.

  7. Curvature and ionization-induced reversible hydrogen storage in metalized hexagonal B{sub 36}

    SciTech Connect

    Liu, Chun-Sheng Wang, Xiangfu; Yan, Xiaohong; Ye, Xiao-Juan; Zeng, Zhi

    2014-11-21

    The synthesis of quasiplanar boron clusters (B{sub 36}) with a central hexagonal hole provides the first experimental evidence that a single-atomic-layer borophene with hexagonal vacancies is potentially viable [Z. Piazza, H. Hu, W. Li, Y. Zhao, J. Li, and L. S. Wang, Nat. Commun. 5, 3113 (2014)]. However, owing to the hexagonal holes, tunning the electronic and physical properties of B{sub 36} through chemical modifications is not fully understood. Based on (van der Waals corrected-) density functional theory, we show that Li adsorbed on B{sub 36} and B{sub 36}{sup −} clusters can serve as reversible hydrogen storage media. The present results indicate that the curvature and ionization of substrates can enhance the bond strength of Li due to the energetically favorable B 2p-Li 2p orbitals hybridization. Both the polarization mechanism and the orbital hybridization between H-s orbitals and Li-2s2p orbitals contribute to the adsorption of H{sub 2} molecules and the resulting adsorption energy lies between the physisorbed and chemisorbed states. Interestingly, the number of H{sub 2} in the hydrogen storage medium can be measured by the appearance of the negative differential resistance behavior at different bias voltage regions. Furthermore, the cluster-assembled hydrogen storage materials constructed by metalized B{sub 36} clusters do not cause a decrease in the number of adsorbed hydrogen molecules per Li. The system reported here is favorable for the reversible hydrogen adsorption/desorption at ambient conditions.

  8. Hydrogen peroxide modification enhances the ability of biochar (hydrochar) produced from hydrothermal carbonization of peanut hull to remove aqueous heavy metals: Batch and column tests

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experimental and modeling investigations were conducted to examine the effect of hydrogen peroxide treatment on hydrothermally produced biochar (hydrochar) from peanut hull to remove aqueous heavy metals. Characterization measurements showed that hydrogen peroxide modification increased the oxygen-c...

  9. A Unique Ternary Semiconductor-(Semiconductor/Metal) Nano-Architecture for Efficient Photocatalytic Hydrogen Evolution.

    PubMed

    Zhuang, Tao-Tao; Liu, Yan; Sun, Meng; Jiang, Shen-Long; Zhang, Ming-Wen; Wang, Xin-Chen; Zhang, Qun; Jiang, Jun; Yu, Shu-Hong

    2015-09-21

    It has been a long-standing demand to design hetero-nanostructures for charge-flow steering in semiconductor systems. Multi-component nanocrystals exhibit multifunctional properties or synergistic performance, and are thus attractive materials for energy conversion, medical therapy, and photoelectric catalysis applications. Herein we report the design and synthesis of binary and ternary multi-node sheath hetero-nanorods in a sequential chemical transformation procedure. As verified by first-principles simulations, the conversion from type-I ZnS-CdS heterojunction into type-II ZnS-(CdS/metal) ensures well-steered collections of photo-generated electrons at the exposed ZnS nanorod stem and metal nanoparticles while holes at the CdS node sheaths, leading to substantially improved photocatalytic hydrogen-evolution performance. PMID:26276905

  10. Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

    NASA Technical Reports Server (NTRS)

    Huang, Cunping (Inventor); T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor)

    2014-01-01

    Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

  11. Hydrogen Storage in metal-modified single-walled carbon nanotubes

    SciTech Connect

    Dr. Ahn

    2004-04-30

    It has been known for over thirty years that potassium-intercalated graphites can readily adsorb and desorb hydrogen at {approx}1 wt% at 77 K. These levels are much higher than can be attained in pure graphite, owing to a larger thermodynamic enthalpy of adsorption. This increased enthalpy may allow hydrogen sorption at higher temperatures. Potassium has other beneficial effects that enable the design of a new material: (a) Increased adsorption enthalpy in potassium-intercalated graphite compared to pure graphite reduces the pressure and increases the temperature required for a given fractional coverage of hydrogen adsorption. We expect the same effects in potassium-intercalated SWNTs. (b) As an intercalant, potassium separates c-axis planes in graphite. Potassium also separates the individual tubes of SWNTs ropes producing swelling and increased surface area. Increased surface area provides more adsorption sites, giving a proportionately higher capacity. The temperature of adsorption depends on the enthalpy of adsorption. The characteristic temperature is roughly the adsorption enthalpy divided by Boltzmann's constant, k{sub B}. For the high hydrogen storage capacity of SWNTs to be achieved at room temperature, it is necessary to increase the enthalpy of adsorption. Our goal for this project was to use metal modifications to the carbon surface of SWNTs in order to address both enhanced adsorption and surface area. For instance, the enthalpy of sorption of hydrogen on KC8 is 450 meV/H{sub 2}, whereas it is 38 meV/H{sub 2} for unmodified SWNTs. By adsorption thermodynamics we expect approximately that the same performance of SWNTs at 77 K will be achieved at a temperature of [450/38] 77 K = 900 K. This is a high temperature, so we expect that adsorption on nearly all the available sites for hydrogen will occur at room temperature under a much lower pressure. This pressure can be estimated conveniently, since the chemical potential of hydrogen is approximately proportional to the logarithm of the pressure. Using 300 K for room temperature, the 100 bar pressure requirement is reduced to exp(-900/300) 100 bar = 5 bar at room temperature. This is in the pressure range used for prior experimental work such as that of Colin and Herold in the late 1960's and early 1970's.

  12. Bifacial Base-Pairing Behaviors of 5-Hydroxyuracil DNA Bases through Hydrogen Bonding and Metal Coordination.

    PubMed

    Takezawa, Yusuke; Nishiyama, Kotaro; Mashima, Tsukasa; Katahira, Masato; Shionoya, Mitsuhiko

    2015-10-12

    A novel bifacial ligand-bearing nucleobase, 5-hydroxyuracil (U(OH) ), which forms both a hydrogen-bonded base pair (U(OH) -A) and a metal-mediated base pair (U(OH) -M-U(OH) ) has been developed. The U(OH) -M-U(OH) base pairs were quantitatively formed in the presence of lanthanide ions such as Gd(III) when U(OH) -U(OH) pairs were consecutively incorporated into DNA duplexes. This result established metal-assisted duplex stabilization as well as DNA-templated assembly of lanthanide ions. Notably, a duplex possessing U(OH) -A base pairs was destabilized by addition of Gd(III) ions. This observation suggests that the hybridization behaviors of the U(OH) -containing DNA strands are altered by metal complexation. Thus, the U(OH) nucleobase with a bifacial base-pairing property holds great promise as a component for metal-responsive DNA materials. PMID:26332356

  13. Reactive coupling of 4-vinylaniline with hydrogen-terminated Si(100) surfaces for electroless metal and "synthetic metal" deposition.

    PubMed

    Xu, D; Kang, E T; Neoh, K G; Tay, A A O

    2004-04-13

    Pristine and resist-patterned Si(100) substrates were etched by aqueous HF to produce hydrogen-terminated silicon (H-Si(100)) surfaces. The H-Si(100) surface was then subjected to UV-induced reactive coupling of 4-vinylaniline (VAn) to produce the VAn monolayer-modified silicon (VAn-Si) surface. The VAn-Si surface was first functionalized with a "synthetic metal" by oxidative graft polymerization of aniline with the aniline moieties of the coupled VAn molecules. The composition and topography of the VAn-Si and polyaniline (PAn)-grafted VAn-Si (PAn-VAn-Si) surfaces were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The doping-undoping (protonation-deprotonation) and redox-coupling (metal reduction) behavior, as well as the electrical conductivity, of the surface-grafted PAn were found to be similar to those of the aniline homopolymer. The VAn-Si surface was also funtionalized by the electroless plating of copper. Not only did the VAn layer provide chemisorption sites for the palladium catalyst, in the absence of prior sensitization by SnCl2, during the electroless plating process, it also served as an adhesion promotion layer and a low-temperature diffusion barrier for the electrolessly deposited copper. Finally, micropatterning of the grafted PAn and of the electrolessly deposited copper were demonstrated on the resist-patterned VAn-Si surfaces. PMID:15875865

  14. Influence of oxygen on permeation of hydrogen isotopes through group 5 metals

    SciTech Connect

    Hatano, Y.; Busnyuk, A.; Alimov, V.; Livshits, A.; Nakamura, Y.; Matsuyama, M.

    2008-07-15

    Group 5 metals (V, Nb and Ta) are potential candidates of tube material in vacuum permeator for tritium recovery from Pb-17Li liquid blanket system. From this viewpoint, the influence of oxygen on the surface reaction rates of hydrogen on V and Ta were examined in an ultra-high vacuum apparatuses at elevated temperatures, and the results were compared with the data on Nb acquired in a previous study. The surface reaction rates of hydrogen on V and Ta, and consequently permeation rates, decreased with increasing oxygen concentration in the bulk as previously observed for Nb. These observations were ascribed to the increase in surface oxygen coverage with increasing bulk oxygen concentration. The weakest influence of oxygen on hydrogen permeation rate was observed for V. The expected permeation rate through V under typical blanket conditions, however, was not necessarily high due to high oxygen solubility in V. The evaluation indicated that the highest permeation rate should be obtained with Nb under typical blanket conditions. (authors)

  15. Understanding hydrogen sorption in a polar metal-organic framework with constricted channels

    NASA Astrophysics Data System (ADS)

    Stern, Abraham C.; Belof, Jonathan L.; Eddaoudi, Mohamed; Space, Brian

    2012-01-01

    A high fidelity molecular model is developed for a metal-organic framework (MOF) with narrow (approximately 7.3 Å) nearly square channels. MOF potential models, both with and neglecting explicit polarization, are constructed. Atomic partial point charges for simulation are derived from both fragment-based and fully periodic electronic structure calculations. The molecular models are designed to accurately predict and retrodict material gas sorption properties while assessing the role of induction for molecular packing in highly restricted spaces. Thus, the MOF is assayed via grand canonical Monte Carlo (GCMC) for its potential in hydrogen storage. The confining channels are found to typically accommodate between two to three hydrogen molecules in close proximity to the MOF framework at or near saturation pressures. Further, the net attractive potential energy interactions are dominated by van der Waals interactions in the highly polar MOF - induction changes the structure of the sorbed hydrogen but not the MOF storage capacity. Thus, narrow channels, while providing reasonably promising isosteric heat values, are not the best choice of topology for gas sorption applications from both a molecular and gravimetric perspective.

  16. Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces.

    PubMed

    Murphy, Colin J; Carrasco, Javier; Lawton, Timothy J; Liriano, Melissa L; Baber, Ashleigh E; Lewis, Emily A; Michaelides, Angelos; Sykes, E Charles H

    2014-07-01

    Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells. PMID:25005297

  17. Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

    2014-07-01

    Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

  18. Design of hydroforming processes for metallic liners used in high pressure hydrogen storage

    SciTech Connect

    Gelin, J.C.; Labergere, C.; Thibaud, S.; Boudeau, N.

    2005-08-05

    Within the framework of an European project concerning hydrogen storage, one analyze the way to manufacture high pressure tanks (700bars) for hydrogen storage, intended to be embarked for using in motor vehicles. These tanks consist of a metallic liner, which ensure a barrier role compared to the hydrogen atoms as well as a part of the mechanical resistance, and of a composite envelope built by filament rolling up which ensures the complementary part of the mechanical resistance. The paper describes the work completed within this framework, on the basis of the simulation of the hydroforming process thanks to the complete control of the process, in volume of fluid injected. One was thus brought to develop an optimization module based on finite element calculations. This optimization module includes MPI library in order to launch several calculations in parallel on a Linux cluster. It consists in seeking the optimal evolution of the fluid volume injected vs. time to obtain a good quality component. In our case, the optimization criterion is based on the variation thickness of the tube and the possible appearance of necking. It is shown that such a way for controlling the process provide the way to get minimal thickness variation, comparatively to standard optimization approaches where the process parameters are discretized through processing time in a more standard way.

  19. Improvement in hydrogen desorption from ?- and ?-MgH2 upon transition-metal doping.

    PubMed

    Hussain, Tanveer; Maark, Tuhina Adit; Chakraborty, Sudip; Ahuja, Rajeev

    2015-08-24

    A thorough study of the structural, electronic, and hydrogen-desorption properties of ?- and ?-MgH2 phases substituted by selected transition metals (TMs) is performed through first-principles calculations based on density functional theory (DFT). The TMs considered herein include Sc, V, Fe, Co, Ni, Cu, Y, Zr, and Nb, which substitute for Mg at a doping concentration of 3.125?% in both the hydrides. This insertion of TMs causes a variation in the cell volumes of ?- and ?-MgH2 . The majority of the TM dopants decrease the lattice constants, with Ni resulting in the largest reduction. From the formation-energy calculations, it is predicted that except for Cu and Ni, the mixing of all the selected TM dopants with the MgH2 phases is exothermic. The selected TMs also influence the stability of both ?- and ?-MgH2 and cause destabilization by weakening the Mg?H bonds. Our results show that doping with certain TMs can facilitate desorption of hydrogen from ?- and ?-MgH2 at much lower temperatures than from their pure forms. The hydrogen adsorption strengths are also studied by density-of-states analysis. PMID:26079892

  20. Hydrogen Assisted Crack in Dissimilar Metal Welds for Subsea Service under Cathodic Protection

    NASA Astrophysics Data System (ADS)

    Bourgeois, Desmond

    Dissimilar metal welds (DMWs) are routinely used in the oil and gas industries for structural joining of high strength steels in order to eliminate the need for post weld heat treatment (PWHT) after field welding. There have been reported catastrophic failures in these DMWs, particularly the AISI 8630 steel - Alloy 625 DMW combination, during subsea service while under cathodic protection (CP). This is due to local embrittlement that occurs in susceptible microstructures that are present at the weld fusion boundary region. This type of cracking is known as hydrogen assisted cracking (HAC) and it is influenced by base/filler metal combination, and welding and PWHT procedures. DMWs of two material combinations (8630 steel -- Alloy 625 and F22 steel -- Alloy 625), produced with two welding procedures (BS1 and BS3) in as welded and PWHT conditions were investigated in this study. The main objectives included: 1) evaluation of the effect of materials composition, welding and PWHT procedures on the gradients of composition, microstructure, and properties in the dissimilar transition region and on the susceptibility to HAC; 2) investigation of the influence of microstructure on the HAC failure mechanism and identification of microstructural constituents acting as crack nucleation and propagation sites; 3) assessment of the applicability of two-step PWHT to improve the resistance to HAC in DMWs; 4) establishment of non-failure criterion for the delayed hydrogen cracking test (DHCT) that is applicable for qualification of DMWs for subsea service under cathodic protection (CP).

  1. In-Situ Cleaning of Metal Cathodes Using a Hydrogen Ion Beam

    SciTech Connect

    Dowell, D.H.; King, F.K.; Kirby, R.E.; Schmerge, J.F.; /SLAC

    2005-09-01

    Improving and maintaining the quantum efficiency (QE) of a metal photocathode in an s-band RF gun requires a process for cleaning the surface. In this type of gun, the cathode is typically installed and the system is vacuum baked to {approx}200 degrees C. If the QE is too low, the cathode is usually cleaned with the UV-drive laser. While laser cleaning does increase the cathode QE, it requires fluences close to the damage threshold and rastering the small diameter beam, both of which can produce nonuniform electron emission and potentially damage the cathode. This paper investigates the efficacy of a low energy hydrogen ion beam to produce high-QE metal cathodes. Measurements of the QE vs. wavelength, surface contaminants using x-ray photoelectron spectroscopy and surface roughness were performed on a copper sample, and the results showed a significant increase in QE after cleaning with a 1keV hydrogen ion beam. The H-ion beam cleaned an area approximately 1cm in diameter and had no effect on the surface roughness while significantly increasing the QE. These results and a comparison with theory as well as a scheme for installing an H-ion cleaner on an s-band gun are presented.

  2. Metal diselenide nanoparticles as highly active and stable electrocatalysts for the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Liang, Jia; Yang, Yingchao; Zhang, Jing; Wu, Jingjie; Dong, Pei; Yuan, Jiangtan; Zhang, Gengmin; Lou, Jun

    2015-09-01

    In this communication, nickel diselenide (NiSe2) nanoparticles are synthesized by a facile and low-cost hydrothermal method. The synthesis method can be extended to other metal diselenides as well. The electrode made of NiSe2 exhibits superior electrocatalytic activity in the hydrogen evolution reaction (HER). A low Tafel slope of 31.1 mV per decade is achieved for NiSe2, which is comparable to that of platinum (~30 mV per decade). Moreover, the catalytic activity of NiSe2 is very stable and no obvious degradation is found even after 1000 cyclic voltammetric sweeps.In this communication, nickel diselenide (NiSe2) nanoparticles are synthesized by a facile and low-cost hydrothermal method. The synthesis method can be extended to other metal diselenides as well. The electrode made of NiSe2 exhibits superior electrocatalytic activity in the hydrogen evolution reaction (HER). A low Tafel slope of 31.1 mV per decade is achieved for NiSe2, which is comparable to that of platinum (~30 mV per decade). Moreover, the catalytic activity of NiSe2 is very stable and no obvious degradation is found even after 1000 cyclic voltammetric sweeps. Electronic supplementary information (ESI) available: Experimental section, additional figures and tables. See DOI: 10.1039/c5nr03724g

  3. First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

    SciTech Connect

    J. Karl Johnson

    2011-05-20

    The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. New materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.

  4. First-Principles Study of Electronic Structure and Hydrogen Adsorption of 3d Transition Metal Exposed Paddle Wheel Frameworks

    SciTech Connect

    Bak, J. H.; Le, V. D.; Kang, J.; Wei, S. H.; Kim, Y. H.

    2012-04-05

    Open-site paddle wheels, comprised of two transition metals bridged with four carboxylate ions, have been widely used for constructing metal-organic frameworks with large surface area and high binding energy sites. Using first-principles density functional theory calculations, we have investigated atomic and electronic structures of various 3d transition metal paddle wheels before and after metal exposure and their hydrogen adsorption properties at open metal sites. Notably, the hydrogen adsorption is impeded by covalent metal-metal bonds in early transition metal paddle wheels from Sc to Cr and by the strong ferromagnetic coupling of diatomic Mn and Fe in the paddle wheel configurations. A significantly enhanced H{sub 2} adsorption is predicted in the nonmagnetic Co{sub 2} and Zn{sub 2} paddle wheel with the binding energy of {approx}0.2 eV per H{sub 2}. We also propose the use of two-dimensional Co{sub 2} and Zn{sub 2} paddle wheel frameworks that could have strongly adsorbed dihydrogen up to 1.35 wt % for noncryogenic hydrogen storage applications.

  5. Boryl-metal bonds facilitate cobalt/nickel-catalyzed olefin hydrogenation.

    PubMed

    Lin, Tzu-Pin; Peters, Jonas C

    2014-10-01

    New approaches toward the generation of late first-row metal catalysts that efficiently facilitate two-electron reductive transformations (e.g., hydrogenation) more typical of noble-metal catalysts is an important goal. Herein we describe the synthesis of a structurally unusual S = 1 bimetallic Co complex, [((Cy)PBP)CoH]2 (1), supported by bis(phosphino)boryl and bis(phosphino)hydridoborane ligands. This complex reacts reversibly with a second equivalent of H2 (1 atm) and serves as an olefin hydrogenation catalyst under mild conditions (room temperature, 1 atm H2). A bimetallic Co species is invoked in the rate-determining step of the catalysis according to kinetic studies. A structurally related Ni(I)Ni(I) dimer, [((Ph)PBP)Ni]2 (3), has also been prepared. Like Co catalyst 1, Ni complex 3 displays reversible reactivity toward H2, affording the bimetallic complex [((Ph)PBHP)NiH]2 (4). This reversible behavior is unprecedented for Ni(I) species and is attributed to the presence of a boryl-Ni bond. Lastly, a series of monomeric ((tBu)PBP)NiX complexes (X = Cl (5), OTf (6), H (7), OC(H)O (8)) have been prepared. The complex ((tBu)PBP)NiH (7) shows enhanced catalytic olefin hydrogenation activity when directly compared with its isoelectronic/isostructural analogues where the boryl unit is substituted by a phenyl or amine donor, a phenomenon that we posit is related to the strong trans influence exerted by the boryl ligand. PMID:25181350

  6. Metal and Precursor Effect during 1-Heptyne Selective Hydrogenation Using an Activated Carbon as Support

    PubMed Central

    Lederhos, Cecilia R.; Badano, Juan M.; Carrara, Nicolas; Coloma-Pascual, Fernando; Almansa, M. Cristina; Liprandi, Domingo; Quiroga, Mnica

    2013-01-01

    Palladium, platinum, and ruthenium supported on activated carbon were used as catalysts for the selective hydrogenation of 1-heptyne, a terminal alkyne. All catalysts were characterized by temperature programmed reduction, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. TPR and XPS suggest that the metal in all catalysts is reduced after the pretreatment with H2 at 673?K. The TPR trace of the PdNRX catalyst shows that the support surface groups are greatly modified as a consequence of the use of HNO3 during the catalyst preparation. During the hydrogenation of 1-heptyne, both palladium catalysts were more active and selective than the platinum and ruthenium catalysts. The activity order of the catalysts is as follows: PdClRX > PdNRX > PtClRX ? RuClRX. This superior performance of PdClRX was attributed in part to the total occupancy of the d electronic levels of the Pd metal that is supposed to promote the rupture of the H2 bond during the hydrogenation reaction. The activity differences between PdClRX and PdNRX catalysts could be attributed to a better accessibility of the substrate to the active sites, as a consequence of steric and electronic effects of the superficial support groups. The order for the selectivity to 1-heptene is as follows: PdClRX = PdNRX > RuClRX > PtClRX, and it can be mainly attributed to thermodynamic effects. PMID:24348168

  7. Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions.

    PubMed

    Rodriguez, Jos A; Illas, Francesc

    2012-01-14

    This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O(2), C(2)H(4), SO(2), thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO(2) at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O(2) and perform the 2CO + O(2)? 2CO(2) reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS(x) catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals. PMID:22108864

  8. Activation of Noble Metals on Metal-Carbide Surfaces: Novel Catalysts for CO Oxidation, Desulfurization and Hydrogenation Reactions

    SciTech Connect

    Rodriguez J. A.; Illas, F.

    2012-01-01

    This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO{sub 2} at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O{sub 2} and perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS{sub x} catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals.

  9. Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

    SciTech Connect

    Ide, Matthew S.; Hao, Bing; Neurock, Matthew; Davis, Robert J.

    2012-04-06

    The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Although Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.

  10. Calcium as a superior coating metal in functionalization of carbon fullerenes for high-capacity hydrogen storage

    SciTech Connect

    Yoon, Mina; Yang, Shenyuan; Hicke, Christian; Wang, Enge; Geohegan, David B; Zhang, Zhenyu

    2008-01-01

    We explore theoretically the feasibility of functionalizing carbon nanostructures for hydrogen storage, focusing on the coating of C60 fullerenes with light alkaline-earth metals. Our first-principles density functional theory studies show that both Ca and Sr can bind strongly to the C60 surface, and highly prefer monolayer coating, thereby explaining existing experimental observations. The strong binding is attributed to an intriguing charge transfer mechanism involving the empty d levels of the metal elements. The charge redistribution, in turn, gives rise to electric fields surrounding the coated fullerenes, which can now function as ideal attractors upon molecular hydrogen adsorption with binding strengths strong enough for potential room temperature applications but weak enough to avoid H2 dissociation. With a hydrogen uptake of >8.4wt% on Ca32C60, Ca is superior to all the recently suggested metal coating elements.

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

    PubMed Central

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

    2016-01-01

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

  12. First-Principles Study on the Grain Boundary Embrittlement of Metals by Solute Segregation: Part II. Metal (Fe, Al, Cu)-Hydrogen (H) Systems

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Masatake; Ebihara, Ken-Ichi; Itakura, Mitsuhiro; Kadoyoshi, Tomoko; Suzudo, Tomoaki; Kaburaki, Hideo

    2011-02-01

    The microscopic mechanism of grain boundary (GB) embrittlement in metals by hydrogen segregation (trapping) has been not well understood for many years. From first-principles calculations, we show here that the calculated cohesive energy of bcc Fe ?3(111) and fcc Al(Cu) ?5(012) symmetrical tilt GBs can be significantly reduced if many hydrogen atoms segregate at the GBs. This indicates that the reduction of the cohesive energy of the GB may cause the hydrogen-induced GB embrittlement in Fe, Al, and Cu. Considering the "mobile" effect of hydrogen during fracture, especially for the Fe system, more hydrogen atoms coming from solid solution state can segregate on the gradually formed two fracture surfaces and reduce further the cohesive energy. We suggest a new idea about the upper and lower critical stresses observed in the constant-load test of hydrogen-induced delayed fracture in high-strength steels; the upper critical stress is determined by the amount (density) of "immobile" hydrogen atoms segregated at the GB before fracture, and the lower critical stress is determined by the total amount (density) of immobile and mobile hydrogen atoms, the latter of which segregate on the two fracture surfaces during fracture.

  13. Hydrogen Interaction with Titanium Carbide-Coated Metals for Fusion Technology Application

    NASA Astrophysics Data System (ADS)

    Caorlin, Marco

    Available from UMI in association with The British Library. The interaction of gaseous hydrogen with TiC coatings deposited on metals by Chemical Vapour Deposition was studied. The prime aim of this study was to determine whether such coatings could affect the rate of absorption and desorption by the metallic substrate. Developing and testing simple models for the experiments in terms of diffusivity D, Sieverts' constant K_{s} and surface reaction rates k_1, k_2, was another goal of the work. Both aims are closely linked to the use of tritium in present and future fusion devices. Two manometric techniques were used. At Ispra, the hydrogen pressure increase in a closed vessel was recorded in time, after loading the sample with hydrogen to equilibrium and evacuating the chamber. Loading pressures between 10^3 Pa and 10^5 Pa were used, with temperatures in the range 673 K-873 K. At Oxford, a similar equilibrium state was perturbed by a imposed periodic volume variation. The corresponding pressure response, in a closed chamber containing the specimen immersed in hydrogen, was recorded in time. Pressures between 4 Pa and 74 Pa were used and the temperature range was 883 K-1083 K. The substrates used were the AISI 316L steel and the molybdenum alloy TZM at Ispra, while only TZM at Oxford. With both methods, a marked increase of the times to reach equilibrium was detected with respect to uncoated samples, while the equilibrium absorption behaviour of the coated specimens was not significantly different from that of the bare ones. Very low diffusivity values were obtained for hydrogen in TiC. For the Ispra samples, the temperature dependence found is D/{rm(m ^2s}^{-1}) = 1.08 times 10^{-12} exp(-{6800 over T/K})while that determined at Oxford, for different TiC specimens, is D/{rm (m^2s}^ {-1}) = 9.60 times 10^{-12} exp (-{6010over T/K}). The surface rate constants determined at Ispra are represented by eqalign {k_1/({rm mol m^{ -2}s^{-1}Pa^{-1}) }&= 4.10 times 10^{-8} exp (-{4560over T/K}), cr k_2/{rm (m^4mol^ {-1}s^{-1})}&= 6.90 times 10^{-12} exp (-{5070 over T/K})cr}and those found at Oxford by eqalign {k_1/({rm mol m^{ -2}s^{-1}Pa^{-1}) }&= 5.40 times 10^{-5} exp (-{10250over T/K}), cr k_2/{rm (m^4mol^ {-1}s^{-1})}&= 2.90 times 10^{-9} exp (-{5070 over T/K}).cr} The Sieverts' constant K_{s } for hydrogen in TiC determined at Oxford is represented by K_{s}/ {rm(mol m^{-3}Pa^ {1/2})} = 2.90 times 10^{ -9} exp (-{5070over T/K }).This gives values lower than for the steel substrate for a factor of 200, and for the TZM substrate for a factor of 2000. The results suggest that TiC would impede hydrogen permeation through steel more effectively in surface-limited regimes. TZM was also studied and was shown to be a possible permeation barrier itself. Trapping was also qualitatively detected in TZM.

  14. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin

    2016-02-01

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm-1 in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm-2 at a low potential of -175 mV and a Tafel slope of 41 mV per decade.

  15. From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

    SciTech Connect

    Studener, F. Müller, K.; Stöhr, M.; Marets, N.; Bulach, V. Hosseini, M. W.

    2015-03-14

    The self-assembly of a metal-free porphyrin bearing two pyridyl coordinating sites and two pentyl chains at trans meso positions was investigated under ultrahigh vacuum on a Ag(111) surface by scanning tunneling microscopy (STM). The STM measurements revealed a well-ordered close-packed structure with a rhombic unit cell for coverages ≤1 monolayer with their molecular plane parallel to the surface. The growth direction of the molecular islands is aligned along the step edges, which are restructured due to molecule-substrate interactions. The shorter unit cell vector of the molecular superstructure follows the 〈1-10〉 direction of the Ag(111) substrate. Hydrogen bonds between pyridyl and pyrrole groups of neighboring molecules as well as weak van der Waals forces between the pentyl chains stabilize the superstructure. Deposition of cobalt atoms onto the close-packed structure at room temperature leads to the formation of a hexagonal porous network stabilized by metal-ligand bonding between the pyridyl ligands and the cobalt atoms. Thermal annealing of the Co-coordination network at temperatures >450 K results in the transformation of the hexagonal network into a second close-packed structure. Changes in the molecule-substrate interactions due to metalation of the porphyrin core with Co as well as intermolecular interactions can explain the observed structural transformations.

  16. From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

    NASA Astrophysics Data System (ADS)

    Studener, F.; Müller, K.; Marets, N.; Bulach, V.; Hosseini, M. W.; Stöhr, M.

    2015-03-01

    The self-assembly of a metal-free porphyrin bearing two pyridyl coordinating sites and two pentyl chains at trans meso positions was investigated under ultrahigh vacuum on a Ag(111) surface by scanning tunneling microscopy (STM). The STM measurements revealed a well-ordered close-packed structure with a rhombic unit cell for coverages ≤1 monolayer with their molecular plane parallel to the surface. The growth direction of the molecular islands is aligned along the step edges, which are restructured due to molecule-substrate interactions. The shorter unit cell vector of the molecular superstructure follows the <1-10> direction of the Ag(111) substrate. Hydrogen bonds between pyridyl and pyrrole groups of neighboring molecules as well as weak van der Waals forces between the pentyl chains stabilize the superstructure. Deposition of cobalt atoms onto the close-packed structure at room temperature leads to the formation of a hexagonal porous network stabilized by metal-ligand bonding between the pyridyl ligands and the cobalt atoms. Thermal annealing of the Co-coordination network at temperatures >450 K results in the transformation of the hexagonal network into a second close-packed structure. Changes in the molecule-substrate interactions due to metalation of the porphyrin core with Co as well as intermolecular interactions can explain the observed structural transformations.

  17. Metallic WO2-Carbon Mesoporous Nanowires as Highly Efficient Electrocatalysts for Hydrogen Evolution Reaction.

    PubMed

    Wu, Rui; Zhang, Jingfang; Shi, Yanmei; Liu, Dali; Zhang, Bin

    2015-06-10

    The development of electrocatalysts to generate hydrogen, with good activity and stability, is a great challenge in the fields of chemistry and energy. Here we demonstrate a "hitting three birds with one stone" method to synthesize less toxic metallic WO2-carbon mesoporous nanowires with high concentration of oxygen vacancies (OVs) via calcination of inorganic/organic WO3-ethylenediamine hybrid precursors. The products exhibit excellent performance for H2 generation: the onset overpotential is only 35 mV, the required overpotentials for 10 and 20 mA/cm(2) are 58 and 78 mV, the Tafel slope is 46 mV/decade, the exchange current density is 0.64 mA/cm(2), and the stability is over 10 h. Further studies, in combination with density functional theory, demonstrate that the unusual electronic structure and the large amount of active sites, generated by the high concentration of OVs, as well as the closely attached carbon materials, were key factors for excellent performance. Our results experimentally and theoretically establish metallic transition metal oxides (TMOs) as intriguing novel electrocatalysts for H2 generation. Such TMOs with OVs might be promising candidates for other energy storage and conversion applications. PMID:25992910

  18. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction.

    PubMed

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin

    2016-01-01

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm(-1) in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm(-2) at a low potential of -175 mV and a Tafel slope of 41 mV per decade. PMID:26861766

  19. In-Situ Cleaning of Metal Cathodes using a Hydrogen Ion Beam

    SciTech Connect

    Dowell, D.H.; King, F.K.; Kirby, R.E.; Schmerge, J.F.; /SLAC

    2006-03-29

    Metal photocathodes are commonly used in high-field RF guns because they are robust, straightforward to implement and tolerate relatively poor vacuum compared to semi-conductor cathodes. However these cathodes have low quantum efficiency (QE) even at UV wavelengths, and still require some form of cleaning after installation in the gun. A commonly used process for improving the QE is laser cleaning. In this technique the UV drive laser is focused to a small diameter close to the metal's damage threshold and then moved across the surface to remove contaminants. This method does improve the QE, but can produce non-uniform emission and potentially damage the cathode. Ideally an alternative process which produces an atomically clean, but unaltered surface is needed. In this paper we explore using a hydrogen ion (H-ion) beam to clean a copper cathode. We describe QE measurements over the wavelength range of interest as a function of integrated exposure to an H-ion beam. We also describe the data analysis to obtain the work function and derive a formula of the QE for metal cathodes. Our measured work function for the cleaned sample is in good agreement with published values, and the theoretical QE as a function of photon wavelength is in excellent agreement with the cleaned copper experimental results. Finally, we propose an in-situ installation of an H-ion gun compatible with existing s-band RF guns.

  20. Density Functional Theory Study of Hydrogen Adsorption in a Ti-Decorated Mg-Based Metal-Organic Framework-74.

    PubMed

    Suksaengrat, Pitphichaya; Amornkitbamrung, Vittaya; Srepusharawoot, Pornjuk; Ahuja, Rajeev

    2016-03-16

    The Ti-binding energy and hydrogen adsorption energy of a Ti-decorated Mg-based metal-organic framework-74 (Mg-MOF-74) were evaluated by using first-principles calculations. Our results revealed that only three Ti adsorption sites were found to be stable. The adsorption site near the metal oxide unit is the most stable. To investigate the hydrogen-adsorption properties of Ti-functionalized Mg-MOF-74, the hydrogen-binding energy was determined. For the most stable Ti adsorption site, we found that the hydrogen adsorption energy ranged from 0.26 to 0.48 eV H2 (-1) . This is within the desirable range for practical hydrogen-storage applications. Moreover, the hydrogen capacity was determined by using ab initio molecular dynamics simulations. Our results revealed that the hydrogen uptake by Ti-decorated Mg-MOF-74 at temperatures of 77, 150, and 298 K and ambient pressure were 1.81, 1.74, and 1.29 H2  wt %, respectively. PMID:26717417

  1. A Phenomenological Study of the Metal-Oxide Interface: The Role of Catalysis in Hydrogen Production from Renewable Resources

    SciTech Connect

    Idriss, H.; Llorca, J; Chan, S; Blackford, M; Pas, S; Hill, A; Alamgir, F; Rettew, R; Petersburg, C; Barteau, M

    2008-01-01

    The truth about Cats: The metal-oxide interface of a Pd-Rh/CeO{sub 2} catalyst was studied in the context of developing active, selective and durable solid catalytic materials for the production of hydrogen from renewables. The presence of a stable contact between finely dispersed transition-metal clusters (Pd and Rh) on the nanoparticles of the CeO{sub 2} support leads to a highly active and stable catalyst for the steam reforming of ethanol.

  2. Effective thermal conductivities of four metal ceramic composite coatings in hydrogen-oxygen rocket firings

    NASA Technical Reports Server (NTRS)

    Schacht, R. L.; Price, H. G., Jr.; Quentmeyer, R. J.

    1972-01-01

    An experimental investigation was conducted to determine the effective conductivities of four plasma-arc-sprayed, metal-ceramic gradated coatings on hydrogen-oxygen thrust chambers. The effective thermal conductivities were not a function of pressure or oxidant-to-fuel ratio. The various materials that made up these composites do not seem to affect the thermal conductivity values as much as the differences in the thermal conductivities of the parent materials would lead one to expect. Contact resistance evolving from the spraying process seems to be the controlling factor. The thermal conductivities of all the composites tested fell in the range of 0.75 to 7.5 watts per meter kelvin.

  3. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide

    PubMed Central

    Nagarkar, Sanjog S.; Saha, Tanmoy; Desai, Aamod V.; Talukdar, Pinaki; Ghosh, Sujit K.

    2014-01-01

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions. PMID:25394493

  4. Postsynthetic modification of metal-organic framework for hydrogen sulfide detection

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Zhang, Jianmin; Hu, Quan; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2015-11-01

    Hydrogen sulfide (H2S) has recently been identified as the third biological gaseous messenger (gasotransmitter) that is involved in regulating many important physiological processes. The detection of H2S is thus essential for its roles but remain challenging in living systems. We report herein a novel turn-on fluorescent probe for H2S detection based on azide functionalized metal-organic framework (MOF). The MOF probe displayed high sensitivity (detection limit, 28.3 ?M), excellent selectivity, and fast response (<2 min) toward H2S over other biologically relevant species. We envisage that this MOF probe can be employed as a useful tool to further elucidate the biological roles of H2S.

  5. Effect of Hydrogen Peroxide Treatment on the Characteristics of Metal/ZnO Contact

    NASA Astrophysics Data System (ADS)

    Kim, Y. S.; Yun, H. J.

    2011-12-01

    Treatment of ZnO surface with H2O2 (hydrogen peroxide) prior to contact deposition was investigated to enhance the performance of Schottky contact. Effects of bare ZnO surface-polarity and metal deposition method on the I-V characteristics were also studied. While a conversion from Ohmic to rectifying behavior is observed for the thermal-evaluated Au on n-type ZnO (0001_) with H2O2 treatment, the diode characteristics are deteriorated by the H2O2 pre-treatment in the Zn-polar case. X-ray photoemission spectroscopy (XPS) and room-temperature photoluminescence (PL) results show that the H2O2 treatment is effective in removing deep-level defects near the Zn-terminated ZnO surface region, but it is not relatively effective for the O-terminated one.

  6. Charge separation technique for metal-oxide-silicon capacitors in the presence of hydrogen deactivated dopants

    SciTech Connect

    WITCZAK,STEVEN C.; WINOKUR,PETER S.; LACOE,RONALD C.; MAYER,DONALD C.

    2000-02-01

    An improved charge separation technique for metal-oxide-silicon (MOS) capacitors is presented which accounts for the deactivation of substrate dopants by hydrogen at elevated irradiation temperatures or small irradiation biases. Using high-frequency capacitance-voltage (C-V) measurements, radiation-induced inversion voltage shifts are separated into components due to oxide trapped charge, interface traps and deactivated dopants, where the latter is computed from a reduction in Si capacitance. In the limit of no radiation-induced dopant deactivation, this approach reduces to the standard midgap charge separation technique used widely for the analysis of room-temperature irradiations. The technique is demonstrated on a p-type MOS capacitor irradiated with {sup 60}Co {gamma}-rays at 100 C and zero bias, where the dopant deactivation is significant.

  7. Methods for producing hydrogen (BI) sulfide and/or removing metals

    DOEpatents

    Truex, Michael J [Richland, WA; Peyton, Brent M [Pullman, WA; Toth, James J [Kennewick, WA

    2002-05-14

    The present invention is a process wherein sulfide production by bacteria is efficiently turned on and off, using pH adjustment. The adjustment of pH impacts sulfide production by bacteria by altering the relative amounts of H.sub.2 S and HS-- in solution and thereby control the inhibition of the bacterial metabolism that produces sulfide. This process can be used to make a bioreactor produce sulfide "on-demand" so that the production of sulfide can be matched to its use as a metal precipitation reagent. The present invention is of significance because it enables the use of a biological reactor, a cost effective sulfide production system, by making the biological reactor produce hydrogen sulfide "on demand", and therefore responsive to production schedules, waste stream generation rate, and health and safety requirements/goals.

  8. Low-temperature thermostatics of face-centered-cubic metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Caron, L. G.

    1974-01-01

    The thermostatic properties of a high-symmetry phase of metallic hydrogen with atomic sphere radius between 0.1 and 1.5 bohr are studied, with special emphasis accorded to electronic screening and quantum proton motion. The electron-proton and proton-proton interactions receive a perturbation treatment based on the Singwi dielectric function, while the proton motion is handled by self-consistent harmonic approximation. Quantum behavior is found to be less pronounced than expected, and nuclear magnetism is absent. The phonon spectrum is, however, affected by screening and large proton motion. The zero-point vibrational energy and the superconducting critical temperature are below previous estimates. The crystalline-defect formation energies are a few times the Debye energy, which implies that defects contribute significantly to melting at the lower particle densities.

  9. Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2016-03-18

    The role of metal free dual catalysis in the hydrogen sulfide (H2 S)-induced activation of carbon dioxide (CO2 ) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2 S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus. PMID:26781129

  10. Rydberg hydrogen atom near a metallic surface: Stark regime and ionization dynamics

    SciTech Connect

    Inarrea, Manuel; Salas, J. Pablo; Lanchares, Victor; Pascual, Ana Isabel; Palacian, Jesus F.; Yanguas, Patricia

    2007-11-15

    We investigate the classical dynamics of a hydrogen atom near a metallic surface in the presence of a uniform electric field. To describe the atom-surface interaction we use a simple electrostatic image model. Owing to the axial symmetry of the system, the z-component of the canonical angular momentum P{sub {phi}} is an integral and the electronic dynamics is modeled by a two degrees of freedom Hamiltonian in cylindrical coordinates. The structure and evolution of the phase space as a function of the electric field strength is explored extensively by means of numerical techniques of continuation of families of periodic orbits and Poincare surfaces of section. We find that, due to the presence of the electric field, the atom is strongly polarized through two consecutive pitchfork bifurcations that strongly change the phase space structure. Finally, by means of the phase space transition state theory and the classical spectral theorem, the ionization dynamics of the atom is studied.

  11. Charge separation technique for metal-oxide-silicon capacitors in the presence of hydrogen deactivated dopants

    SciTech Connect

    Witczak, Steven C.; Winokur, Peter S.; Lacoe, Ronald C.; Mayer, Donald C.

    2000-06-01

    An improved charge separation technique for metal-oxide-silicon (MOS) capacitors is presented which accounts for the deactivation of substrate dopants by hydrogen at elevated irradiation temperatures or small irradiation biases. Using high-frequency capacitance-voltage measurements, radiation-induced inversion voltage shifts are separated into components due to oxide trapped charge, interface traps, and deactivated dopants, where the latter is computed from a reduction in Si capacitance. In the limit of no radiation-induced dopant deactivation, this approach reduces to the standard midgap charge separation technique used widely for the analysis of room-temperature irradiations. The technique is demonstrated on a p-type MOS capacitor irradiated with {sup 60}Co {gamma} rays at 100 degree sign C and zero bias, where the dopant deactivation is significant.(c) 2000 American Institute of Physics.

  12. Final LDRD report : metal oxide films, nanostructures, and heterostructures for solar hydrogen production.

    SciTech Connect

    Kronawitter, Coleman X.; Antoun, Bonnie R.; Mao, Samuel S.

    2012-01-01

    The distinction between electricity and fuel use in analyses of global power consumption statistics highlights the critical importance of establishing efficient synthesis techniques for solar fuels-those chemicals whose bond energies are obtained through conversion processes driven by solar energy. Photoelectrochemical (PEC) processes show potential for the production of solar fuels because of their demonstrated versatility in facilitating optoelectronic and chemical conversion processes. Tandem PEC-photovoltaic modular configurations for the generation of hydrogen from water and sunlight (solar water splitting) provide an opportunity to develop a low-cost and efficient energy conversion scheme. The critical component in devices of this type is the PEC photoelectrode, which must be optically absorptive, chemically stable, and possess the required electronic band alignment with the electrochemical scale for its charge carriers to have sufficient potential to drive the hydrogen and oxygen evolution reactions. After many decades of investigation, the primary technological obstacle remains the development of photoelectrode structures capable of efficient conversion of light with visible frequencies, which is abundant in the solar spectrum. Metal oxides represent one of the few material classes that can be made photoactive and remain stable to perform the required functions.

  13. Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

    SciTech Connect

    Kennedy, RD; Krungleviciute, V; Clingerman, DJ; Mondloch, JE; Peng, Y; Wilmer, CE; Sarjeant, AA; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK; Mirkin, CA

    2013-09-10

    A Cu-carborane-based metal organic framework (MOF), NU-135, which contains a quasi-spherical para-carborane moiety, has been synthesized and characterized. NU-135 exhibits a pore volume of 1.02 cm(3)/g and a gravimetric BET surface area of ca. 2600 m(2)/g, and thus represents the first highly porous carborane-based MOF. As a consequence of the, unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m(2)/cm(3). CH4, CO2, and H-2 adsorption isotherms were measured over a broad range of pressures and temperatures and are in good agreement with computational predictions. The methane storage capacity of NU-135 at 35 bar and 298 K is ca. 187 v(STP)/v. At 298 K, the pressure required to achieve a methane storage density comparable to that of a compressed natural gas (CNG) tank pressurized to 212 bar, which is a typical storage pressure, is only 65 bar. The methane working capacity (5-65 bar) is 170 v(STP)/v. The volumetric hydrogen storage capacity at 55 bar and 77 K is 49 g/L. These properties are comparable to those of current record holders in the area of methane and hydrogen storage. This initial example lays the groundwork for carborane-based materials with high surface areas.

  14. Hydrogen segregation and its roles in structural stability and metallization: silane under pressure

    NASA Astrophysics Data System (ADS)

    Cui, Wenwen; Shi, Jingming; Liu, Hanyu; Yao, Yansun; Wang, Hui; Iitaka, Toshiaki; Ma, Yanming

    2015-08-01

    We present results from first-principles calculations on silane (SiH4) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241?GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH4 structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H2 units. The H2 units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH4. An interesting outcome of the present study is that the enthalpy sum of SiH4 (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si2H6) between 200 and 300?GPa (for all previously predicted crystalline forms of Si2H6), which calls for a revisit of the stability of Si2H6 under high pressure.

  15. Hydrogen gas sensor based on metal oxide nanoparticles decorated graphene transistor.

    PubMed

    Zhang, Zhangyuan; Zou, Xuming; Xu, Lei; Liao, Lei; Liu, Wei; Ho, Johnny; Xiao, Xiangheng; Jiang, Changzhong; Li, Jinchai

    2015-06-14

    In this work, in order to enhance the performance of graphene gas sensors, graphene and metal oxide nanoparticles (NPs) are combined to be utilized for high selectivity and fast response gas detection. Whether at the relatively optimal temperature or even room temperature, our gas sensors based on graphene transistors, decorated with SnO2 NPs, exhibit fast response and short recovery times (?1 seconds) at 50 C when the hydrogen concentration is 100 ppm. Specifically, X-ray photoelectron spectroscopy and conductive atomic force microscopy are employed to explore the interface properties between graphene and SnO2 NPs. Through the complimentary characterization, a mechanism based on charge transfer and band alignment is elucidated to explain the physical originality of these graphene gas sensors: high carrier mobility of graphene and small energy barrier between graphene and SnO2 NPs have ensured a fast response and a high sensitivity and selectivity of the devices. Generally, these gas sensors will facilitate the rapid development of next-generation hydrogen gas detection. PMID:25978618

  16. Hydrogen segregation and its roles in structural stability and metallization: silane under pressure

    PubMed Central

    Cui, Wenwen; Shi, Jingming; Liu, Hanyu; Yao, Yansun; Wang, Hui; Iitaka, Toshiaki; Ma, Yanming

    2015-01-01

    We present results from first-principles calculations on silane (SiH4) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241 GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH4 structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H2 units. The H2 units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH4. An interesting outcome of the present study is that the enthalpy sum of SiH4 (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si2H6) between 200 and 300 GPa (for all previously predicted crystalline forms of Si2H6), which calls for a revisit of the stability of Si2H6 under high pressure. PMID:26266340

  17. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution.

    PubMed

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E; Kung, Chung-Wei; So, Monica; Sampson, Matthew D; Peters, Aaron W; Kubiak, Cliff P; Farha, Omar K; Hupp, Joseph T

    2015-01-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200?mV at a benchmark current density of 10?mA?cm(-2). Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst. PMID:26365764

  18. Enhanced Photochemical Hydrogen Production by a Molecular Diiron Catalyst Incorporated into a MetalOrganic Framework

    PubMed Central

    2013-01-01

    A molecular proton reduction catalyst [FeFe](dcbdt)(CO)6 (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metalorganic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)3]2+ as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)6 catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1 and 12 from undesirable charge recombination with oxidized ascorbate. PMID:24116734

  19. Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

    SciTech Connect

    Wahiduzzaman, Mohammad; Walther, Christian F. J.; Heine, Thomas

    2014-08-14

    The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H{sub 2}-host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory and the Grand-Canonical Monte Carlo methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the GC-QLDFT. The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H{sub 2} in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18, and MOF-177. Finally, we discuss the evolution of the H{sub 2} quantum fluid with increasing pressure and lowering temperature.

  20. Hydrogen segregation and its roles in structural stability and metallization: silane under pressure.

    PubMed

    Cui, Wenwen; Shi, Jingming; Liu, Hanyu; Yao, Yansun; Wang, Hui; Iitaka, Toshiaki; Ma, Yanming

    2015-01-01

    We present results from first-principles calculations on silane (SiH4) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241?GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH4 structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H2 units. The H2 units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH4. An interesting outcome of the present study is that the enthalpy sum of SiH4 (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si2H6) between 200 and 300?GPa (for all previously predicted crystalline forms of Si2H6), which calls for a revisit of the stability of Si2H6 under high pressure. PMID:26266340

  1. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm-2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  2. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    PubMed Central

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst. PMID:26365764

  3. Metal-Free Hydrogenation Catalyzed by an Air-Stable Borane: Use of Solvent as a Frustrated Lewis Base**

    PubMed Central

    Scott, Daniel J; Fuchter, Matthew J; Ashley, Andrew E

    2014-01-01

    In recent years frustrated Lewis pairs (FLPs) have been shown to be effective metal-free catalysts for the hydrogenation of many unsaturated substrates. Even so, limited functional-group tolerance restricts the range of solvents in which FLP-mediated reactions can be performed, with all FLP-mediated hydrogenations reported to date carried out in non-donor hydrocarbon or chlorinated solvents. Herein we report that the bulky Lewis acids B(C6Cl5)x(C6F5)3?x (x=03) are capable of heterolytic H2 activation in the strong-donor solvent THF, in the absence of any additional Lewis base. This allows metal-free catalytic hydrogenations to be performed in donor solvent media under mild conditions; these systems are particularly effective for the hydrogenation of weakly basic substrates, including the first examples of metal-free catalytic hydrogenation of furan heterocycles. The air-stability of the most effective borane, B(C6Cl5)(C6F5)2, makes this a practically simple reaction method. PMID:25113014

  4. Platinum-nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving.

    PubMed

    Li, Zhi; Yu, Rong; Huang, Jinglu; Shi, Yusheng; Zhang, Diyang; Zhong, Xiaoyan; Wang, Dingsheng; Wu, Yuen; Li, Yadong

    2015-01-01

    Developing catalysts that provide the effective activation of hydrogen and selective absorption of substrate on metal surface is crucial to simultaneously improve activity and selectivity of hydrogenation reaction. Here we present an unique in situ etching and coordination synthetic strategy for exploiting a functionalized metal-organic framework to incorporate the bimetallic platinum-nickel frames, thereby forming a frame within frame nanostructure. The as-grown metal-organic framework serves as a 'breath shell' to enhance hydrogen enrichment and activation on platinum-nickel surface. More importantly, this framework structure with defined pores can provide the selective accessibility of molecules through its one-dimensional channels. In a mixture containing four olefins, the composite can selectively transport the substrates smaller than its pores to the platinum-nickel surface and catalyse their hydrogenation. This molecular sieve effect can be also applied to selectively produce imines, which are important intermediates in the reductive imination of nitroarene, by restraining further hydrogenation via cascade processes. PMID:26391605

  5. Platinum–nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving

    PubMed Central

    Li, Zhi; Yu, Rong; Huang, Jinglu; Shi, Yusheng; Zhang, Diyang; Zhong, Xiaoyan; Wang, Dingsheng; Wu, Yuen; Li, Yadong

    2015-01-01

    Developing catalysts that provide the effective activation of hydrogen and selective absorption of substrate on metal surface is crucial to simultaneously improve activity and selectivity of hydrogenation reaction. Here we present an unique in situ etching and coordination synthetic strategy for exploiting a functionalized metal-organic framework to incorporate the bimetallic platinum–nickel frames, thereby forming a frame within frame nanostructure. The as-grown metal-organic framework serves as a ‘breath shell' to enhance hydrogen enrichment and activation on platinum–nickel surface. More importantly, this framework structure with defined pores can provide the selective accessibility of molecules through its one-dimensional channels. In a mixture containing four olefins, the composite can selectively transport the substrates smaller than its pores to the platinum–nickel surface and catalyse their hydrogenation. This molecular sieve effect can be also applied to selectively produce imines, which are important intermediates in the reductive imination of nitroarene, by restraining further hydrogenation via cascade processes. PMID:26391605

  6. Hydrogen purifier module with membrane support

    DOEpatents

    A hydrogen purifier utilizing a hydrogen-permeable membrane to purify hydrogen from mixed gases containing hydrogen is disclosed. Improved mechanical support for the permeable membrane is described, enabling forward or reverse differential pressurization of the membrane, which further stabilizes the membrane from wrinkling upon hydrogen uptake.

    2012-07-24

    A hydrogen purifier utilizing a hydrogen-permeable membrane to purify hydrogen from mixed gases containing hydrogen is disclosed. Improved mechanical support for the permeable membrane is described, enabling forward or reverse differential pressurization of the membrane, which further stabilizes the membrane from wrinkling upon hydrogen uptake.

  7. B(C6F5)3-catalyzed metal-free hydrogenation of 3,6-diarylpyridazines.

    PubMed

    Wang, Wei; Meng, Wei; Du, Haifeng

    2016-04-14

    This paper describes the first metal-free hydrogenation of 3,6-diarylpyridazines, which was successfully realized using B(C6F5)3 as a catalyst. A variety of 1,4,5,6-tetrahydropyridazine derivatives were furnished in 85-95% yields. PMID:26650120

  8. Electric dipole polarizabilities at imaginary frequencies for hydrogen, the alkali-metal, alkaline-earth, and noble gas atoms

    SciTech Connect

    Derevianko, Andrei Porsev, Sergey G. Babb, James F.

    2010-05-15

    The electric dipole polarizabilities evaluated at imaginary frequencies for hydrogen, the alkali-metal atoms, the alkaline-earth atoms, and the noble gases are tabulated along with the resulting values of the atomic static polarizabilities, the atom-surface interaction constants, and the dispersion (or van der Waals) constants for the homonuclear and the heteronuclear diatomic combinations of the atoms.

  9. Modifications of boronic ester pro-chelators triggered by hydrogen peroxide tune reactivity to inhibit metal-promoted oxidative stress.

    PubMed

    Charkoudian, Louise K; Pham, David M; Kwon, Ashley M; Vangeloff, Abbey D; Franz, Katherine J

    2007-11-21

    Several new analogs of salicylaldehyde isonicotinoyl hydrazone (SIH) and salicylaldehyde benzoyl hydrazone (SBH) that contain an aryl boronic ester (BSIH, BSBH) or acid (BASIH) in place of an aryl hydroxide have been synthesized and characterized as masked metal ion chelators. These pro-chelators show negligible interaction with iron(III), although the boronic acid versions exhibit some interaction with copper(II), zinc(II) and nickel(II). Hydrogen peroxide oxidizes the aryl boronate to phenol, thus converting the pro-chelators to tridentate ligands with high affinity metal binding properties. An X-ray crystal structure of a bis-ligated iron(III) complex, [Fe(SBH(m-OMe)(3))(2)]NO(3), confirms the meridonal binding mode of these ligands. Modifications of the aroyl ring of the chelators tune their iron affinity, whereas modifications on the boron-containing ring of the pro-chelators attenuate their reaction rates with hydrogen peroxide. Thus, the methoxy derivative pro-chelator (p-OMe)BASIH reacts with hydrogen peroxide nearly 5 times faster than the chloro derivative (m-Cl)BASIH. Both the rate of pro-chelator to chelator conversion as well as the metal binding affinity of the chelator influence the overall ability of these molecules to inhibit hydroxyl radical formation catalyzed by iron or copper in the presence of hydrogen peroxide and ascorbic acid. This pro-chelator strategy has the potential to improve the efficacy of medicinal chelators for inhibiting metal-promoted oxidative stress. PMID:17992288

  10. Photoelectrochemical water splitting for hydrogen production with metal oxide (hematite and cupric oxide) based photocatalysts

    NASA Astrophysics Data System (ADS)

    Tang, Houwen

    Solar hydrogen is one ideal energy source to replace fossil fuel, as it is sustainable and environmentally friendly. Solar hydrogen can be generated in a number of ways. Photoelectrochemical (PEC) water splitting is one of the most promising methods for solar-to-chemical energy conversion. In this research project, metal oxide-based photocatalysts, especially hematite (α-Fe 2O3) and cupric oxide (CuO), were investigated for use as electrodes in PEC water splitting for solar hydrogen production. In our research project of hematite-based electrodes, we started with the incorporation of transition metal, particularly titanium (Ti), in hematite thin films to modify the valence and conduction band edges of hematite. We found that Ti impurities improve the electron conductivity of hematite and consequently lead to significantly enhanced photocurrents. We further investigated the Ti and Mg co-alloyed hematite. In this case, Ti is the donor and Mg is the acceptor in hematite. The co-alloying approach enhanced the solubility of Mg and Ti, which led to reduced electron effective mass and therefore increased electron mobility. Also, co-alloying tunes the carrier density and therefore allows the optimization of electrical conductivity. The densities of charged defects were found to be reduced, and therefore carrier recombinations were reduced. As a result, the Ti and Mg co-alloyed hematite thin films exhibited much improved performance in PEC water splitting as compared to pure hematite thin films. For the study of cupric oxide-based electrodes, we first investigated the possibility of reducing the electrode corrosion of cupric oxide in aqueous solutions by incorporating Ti as an electrode corrosion inhibitor. We found that Ti alloying can enhance the stability of cupric oxide in base solutions at the cost of reducing its crystallinity and optical absorption, and consequently lowering its photon-to-electron conversion efficiency. In order to balance the stability and the generated photocurrent, we developed a two-layer structure in which a thin layer of Cu-Ti-O was deposited on bare CuO thin film as a protective layer. Our experimental results indicated that this two-layer structure has an ideal thickness for the protection layer and is suitable for high-performance and long-term application for PEC water splitting.

  11. Ultrafine Metal Phosphide Nanocrystals in Situ Decorated on Highly Porous Heteroatom-Doped Carbons for Active Electrocatalytic Hydrogen Evolution.

    PubMed

    Zhu, Yun-Pei; Xu, Xueyan; Su, Huan; Liu, Yu-Ping; Chen, Tiehong; Yuan, Zhong-Yong

    2015-12-30

    In spite of being technologically feasible, electrochemical water reduction to facilitate hydrogen production is confronted with issues mainly due to the lack of affordable and efficient catalysts for the water reduction half reaction. Reported herein is the fabrication of metal phosphides nanocrystals uniformly loaded on highly porous heteroatom-modified carbons through one-step carbonization-phosphization methodology. Remarkably, the well-structured porosity and the increased electrochemically accessible active sites ensure the high catalytic efficiency for electrochemical hydrogen evolution in acidic medium in terms of small onset potentials (33 mV) and large cathodic current density (0.481 mA cm(-2)), even comparable to the state-of-the-art Pt/C benchmark. The easily prepared composite catalysts of structural and textural peculiarities may serve as promising non-noble metal catalysts for realistic hydrogen evolution. PMID:26633079

  12. AB initio free energy calculations of the solubility of silica in metallic hydrogen and application to giant planet cores

    SciTech Connect

    González-Cataldo, F.; Wilson, Hugh F.; Militzer, B.

    2014-05-20

    By combining density functional molecular dynamics simulations with a thermodynamic integration technique, we determine the free energy of metallic hydrogen and silica, SiO{sub 2}, at megabar pressures and thousands of degrees Kelvin. Our ab initio solubility calculations show that silica dissolves into fluid hydrogen above 5000 K for pressures from 10 and 40 Mbars, which has implications for the evolution of rocky cores in giant gas planets like Jupiter, Saturn, and a substantial fraction of known extrasolar planets. Our findings underline the necessity of considering the erosion and redistribution of core materials in giant planet evolution models, but they also demonstrate that hot metallic hydrogen is a good solvent at megabar pressures, which has implications for high-pressure experiments.

  13. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction

    PubMed Central

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-pin

    2016-01-01

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal–metal Raman stretching mode at 146 cm−1 in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm−2 at a low potential of −175 mV and a Tafel slope of 41 mV per decade. PMID:26861766

  14. Precipitation of heavy metals from coal ash leachate using biogenic hydrogen sulfide generated from FGD gypsum.

    PubMed

    Jayaranjan, Madawala Liyanage Duminda; Annachhatre, Ajit P

    2013-01-01

    Investigations were undertaken to utilize flue gas desulfurization (FGD) gypsum for the treatment of leachate from the coal ash (CA) dump sites. Bench-scale investigations consisted of three main steps namely hydrogen sulfide (H(2)S) production by sulfate reducing bacteria (SRB) using sulfate from solubilized FGD gypsum as the electron acceptor, followed by leaching of heavy metals (HMs) from coal bottom ash (CBA) and subsequent precipitation of HMs using biologically produced sulfide. Leaching tests of CBA carried out at acidic pH revealed the existence of several HMs such as Cd, Cr, Hg, Pb, Mn, Cu, Ni and Zn. Molasses was used as the electron donor for the biological sulfate reduction (BSR) process which produced sulfide rich effluent with concentration up to 150 mg/L. Sulfide rich effluent from the sulfate reduction process was used to precipitate HMs as metal sulfides from CBA leachate. HM removal in the range from 40 to 100% was obtained through sulfide precipitation. PMID:23168629

  15. Flexible Sandwich Diaphragms Are Less Permeable

    NASA Technical Reports Server (NTRS)

    Michalovic, John G.; Vassallo, Franklin A.

    1993-01-01

    Diaphragms for use in refrigerator compressors made as laminates of commercially available elastomers and metals. Diaphragms flexible, but less permeable by chlorofluorocarbon refrigerant fluids than diaphragms made of homogeneous mixtures of materials.

  16. The influence of hydrogen peroxide and histamine on lung permeability and translocation of iridium nanoparticles in the isolated perfused rat lung

    PubMed Central

    Meiring, James J; Borm, Paul JA; Bagate, Karim; Semmler, Manuela; Seitz, Jürgen; Takenaka, Shinji; Kreyling, Wolfgang G

    2005-01-01

    Background Translocation of ultrafine particles (UFP) into the blood that returns from the lungs to the heart has been forwarded as a mechanism for particle-induced cardiovascular effects. The objective of this study was to evaluate the role of the endothelial barrier in the translocation of inhaled UFP from the lung into circulation. Methods The isolated perfused rat lung (IPRL) was used under negative pressure ventilation, and radioactive iridium particles (18 nm, CMD, 192Ir-UFP) were inhaled during 60 minutes to achieve a lung burden of 100 – 200 μg. Particle inhalation was done under following treatments: i) control perfusion, ii) histamine (1 μM in perfusate, iii) luminal histamine instillation (1 mM), and iv) luminal instillation of H2O2. Particle translocation to the perfusate was assessed by the radioactivity of 192Ir isotope. Lung permeability by the use of Tc99m-labeled diethylene triamine pentaacetic acid (DTPA). In addition to light microscopic morphological evaluation of fixed lungs, alkaline phosphatase (AKP) and angiotensin converting enzyme (ACE) in perfusate were measured to assess epithelial and endothelial integrity. Results Particle distribution in the lung was homogenous and similar to in vivo conditions. No translocation of Ir particles at negative pressure inhalation was detected in control IPL, but lungs pretreated with histamine (1 μM) in the perfusate or with luminal H2O2 (0.5 mM) showed small amounts of radioactivity (2–3 % dose) in the single pass perfusate starting at 60 min of perfusion. Although the kinetics of particle translocation were different from permeability for 99mTc-DTPA, the pretreatments (H2O2, vascular histamine) caused similar changes in the translocation of particles and soluble mediator. Increased translocation through epithelium and endothelium with a lag time of one hour occurred in the absence of epithelial and endothelial damage. Conclusion Permeability of the lung barrier to UFP or nanoparticles is controlled both at the epithelial and endothelial level. Conditions that affect this barrier function such as inflammation may affect translocation of NP. PMID:15982423

  17. Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions

    SciTech Connect

    Mader, Elizabeth A.; Manner, Virginia W.; Markle, Todd F.; Wu, Adam; Franz, James A.; Mayer, James M.

    2009-03-10

    Reported herein are thermochemical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors MIILH and oxyl radicals. [FeII(H2bip)3]2+, [FeII(H2bim)3]2+, [CoII(H2bim)3]2+ and RuII(acac)2(py-imH) [H2bip = 2,2’-bi-1,4,5,6-tetrahydro¬pyrimidine, H2bim = 2,2’-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2’-pyridyl)¬imidazole)] each react with TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) or tBu3PhO• (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex MIIIL, and TEMPOH or tBu3PhOH. Solution equilibrium measurements for the reactions of Co and Fe complexes with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer: ΔSºHAT = -30 ± 2 cal mol-1 K-1 for the two iron complexes and -41 ± 2 cal mol-1 K-1 for [CoII(H2bim)3]2+. The ΔSºHAT for TEMPO + RuII(acac)2(py-imH) is much closer to zero, 4.9 ± 1.1 cal mol-1 K-1. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [FeII(H2bip)3]2+ + TEMPO, thus also confirming ΔSºHAT. Calorimetry on TEMPOH + tBu3PhO• gives ΔHºHAT = 11.2 ± 0.5 kcal mol-1 which matches the enthalpy predicted from the difference in literature solution BDEs. An evaluation of the literature BDEs of both TEMPOH and tBu3PhOH is briefly presented and new estimates are included on the relative enthalpy of solvation for tBu3PhO• vs. tBu3PhOH. The primary contributor to the large magnitude of the ground-state entropy |ΔSºHAT| for the metal complexes is vibrational entropy, ΔSºvib. The common assumption that ΔSºHAT ≈ 0 for HAT reactions, developed for organic and small gas phase molecules, does not hold for transition metal based HAT reactions. The trend in magnitude of |ΔSºHAT| for reactions with TEMPO, RuII(acac)2(py-imH) << [FeII(H2bip)3]2+ = [FeII(H2bim)3]2+ < [CoII(H2bim)3]2+, is surprisingly well predicted by the trends for electron transfer half-reaction entropies, ΔSºET, in aprotic solvents. ΔSºET and ΔSºHAT are both affected by ΔSºvib and vary significantly with the metal center involved. The close connection between ΔSºHAT and ΔSºET provides an important link between these two fields and provides a starting point from which to predict which HAT systems will have important ground-state entropy effects. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  18. Polymer/Silicate Nanocomposites Used to Manufacture Gas Storage Tanks With Reduced Permeability

    NASA Technical Reports Server (NTRS)

    Campbell, Sandi G.; Johnston, Chris

    2004-01-01

    Over the past decade, there has been considerable research in the area of polymer-layered silicate nanocomposites. This research has shown that the dispersion of small amounts of an organically modified layered silicate improves the polymer strength, modulus, thermal stability, and barrier properties. There have been several reports on the dispersion of layered silicates in an epoxy matrix. Potential enhancements to the barrier properties of epoxy/silicate nanocomposites make this material attractive for low permeability tankage. Polymer matrix composites (PMCs) have several advantages for cryogenic storage tanks. They are lightweight, strong, and stiff; therefore, a smaller fraction of a vehicle's potential payload capacity is used for propellant storage. Unfortunately, the resins typically used to make PMC tanks have higher gas permeability than metals. This can lead to hydrogen loss through the body of the tank instead of just at welds and fittings. One approach to eliminate this problem is to build composite tanks with thin metal liners. However, although these tanks provide good permeability performance, they suffer from a substantial mismatch in the coefficient of thermal expansion, which can lead to failure of the bond between the liner and the body of the tank. Both problems could be addressed with polymersilicate nanocomposites, which exhibit reduced hydrogen permeability, making them potential candidates for linerless PMC tanks. Through collaboration with Northrop Grumman and Michigan State University, nanocomposite test tanks were manufactured for the NASA Glenn Research Center, and the helium permeability was measured. An organically modified silicate was prepared at Michigan State University and dispersed in an epoxy matrix (EPON 826/JeffamineD230). The epoxy/silicate nanocomposites contained either 0 or 5 wt% of the organically modified silicate. The tanks were made by filament winding carbon fibers with the nanocomposite resin. Helium permeability was measured by Northrop Grumman, showing that the leak rate/day of the nanocomposite matrix tank was approximately 80-percent less than that of the neat epoxy matrix tank.

  19. Measuring Permeability of Composite Cryotank Laminants

    NASA Technical Reports Server (NTRS)

    Oliver, Stanley T.; Selvidge, Shawn; Watwood, Michael C.

    2004-01-01

    This paper describes a test method developed to identify whether certain materials and material systems are suitable candidates for large pressurized reusable cryogenic tanks intended for use in current and future manned launch systems. It provides a quick way to screen numerous candidate materials for permeability under anticipated loading environments consistent with flight conditions, as well as addressing reusability issues. cryogenic tank, where the major design issue was hydrogen permeability. It was successfully used to evaluate samples subjected to biaxial loading while maintaining test temperatures near liquid hydrogen. After each sample was thermally preconditioned, a cyclic pressure load was applied to simulate the in-plane strain. First permeability was measured while a sample was under load. Then the sample was unloaded and allowed to return to ambient temperature. The test was repeated to simulate reusability, in order to evaluate its effects on material permeability.

  20. The use of palladium to obtain reproducible boundary conditions for permeability measurements using galvanostatic charging

    NASA Astrophysics Data System (ADS)

    Bowker, J.; Piercy, G. R.

    1985-05-01

    The diffusion current of hydrogen through palladium in an electrochemical cell initially rises linearly with the charging current, reaches a steady “plateau” value, and then rises again. The diffusivity of hydrogen in palladium was measured using standard transient techniques in the initial region of low current density. Combining this value with the measured value of diffusion current at the plateau level gave a concentration of hydrogen at the entrance surface of the palladium that was the same for three different palladium thicknesses, and was equal to the saturation value in α palladium. It is proposed that this can be used as a known and reproducible effective hydrogen pressure (0.019 atm) if palladium is plated onto other metals before measuring their permeability in an electrochemical cell. Experimental evidence for this was obtained from permeability measurements made on several thicknesses of iron. Permeation studies were also made on AISI 410 stainless steel and tin plated mild steel. The measured value for electrolytic tinplate was 107 times that expected from extrapolation of high temperature data. This could be attributed to grain boundaries or porosity covering 0.003 pct of the area. The permeability values of iron and stainless steel are 8.4 x 1012 and 2.8 x 1013 H atom/cm • s • √atm, respectively.

  1. Correlation of Gas Permeability in a Metal-Organic Framework MIL-101(Cr)–Polysulfone Mixed-Matrix Membrane with Free Volume Measurements by Positron Annihilation Lifetime Spectroscopy (PALS)

    PubMed Central

    Jeazet, Harold B. Tanh; Koschine, Tönjes; Staudt, Claudia; Raetzke, Klaus; Janiak, Christoph

    2013-01-01

    Hydrothermally stable particles of the metal-organic framework MIL-101(Cr) were incorporated into a polysulfone (PSF) matrix to produce mixed-matrix or composite membranes with excellent dispersion of MIL-101 particles and good adhesion within the polymer matrix. Pure gas (O2, N2, CO2 and CH4) permeation tests showed a significant increase of gas permeabilities of the mixed-matrix membranes without any loss in selectivity. Positron annihilation lifetime spectroscopy (PALS) indicated that the increased gas permeability is due to the free volume in the PSF polymer and the added large free volume inside the MIL-101 particles. The trend of the gas transport properties of the composite membranes could be reproduced by a Maxwell model. PMID:24957061

  2. The corrosion behavior of Alloy 52 weld metal in cyclic hydrogenated and oxygenated water chemistry in high temperature aqueous environment

    NASA Astrophysics Data System (ADS)

    Xu, Jian; Shoji, Tetsuo

    2015-06-01

    The corrosion behavior of Alloy 52 weld metal in cyclic hydrogenated and oxygenated water chemistry in high temperature water is studied by in situ monitoring corrosion potential (Ecorr), contact electric resistance (CER) and electrochemical impedance measurements (EIS), and ex situ scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis. The Ecorr and film resistance show large change when the environment is changed from hydrogenated water to oxygenated water and changeable with changing environment while the morphology and composition only show obvious distinction in the first cycle. The main factor controlling the electric/electrochemical properties of the oxide film is Ecorr.

  3. Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions

    PubMed Central

    Mader, Elizabeth A.; Manner, Virginia W.; Markle, Todd F.; Wu, Adam; Franz, James A.; Mayer, James M.

    2009-01-01

    Reported herein are thermochemical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors MIILH and oxyl radicals. [FeII(H2bip)3]2+, [FeII(H2bim)3]2+, [CoII(H2bim)3]2+ and RuII(acac)2(py-imH) [H2bip = 2,2-bi-1,4,5,6-tetrahydropyrimidine, H2bim = 2,2-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2-pyridyl)-imidazole)] each react with TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) or tBu3PhO (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex MIIIL, and TEMPOH or tBu3PhOH. Solution equilibrium measurements for the reaction of [CoII(H2bim)3]2+ with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer, ?41 2 cal mol?1 K?1. This is even more negative than the ?SoHAT = ?30 2 cal mol?1 K?1 for the two iron complexes and the ?SoHAT for RuII(acac)2(py-imH) + TEMPO, 4.9 1.1 cal mol?1 K?1, as reported earlier. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [FeII(H2bip)3]2+ + TEMPO, thus also confirming ?SoHAT. Calorimetry on TEMPOH + tBu3PhO gives ?HoHAT = ?11.2 0.5 kcal mol?1 which matches the enthalpy predicted from the difference in literature solution BDEs. A brief evaluation of the literature thermochemistry of TEMPOH and tBu3PhOH supports the common assumption that ?SoHAT ? 0 for HAT reactions of organic and small gas-phase molecules. However, this assumption does not hold for transition metal based HAT reactions. The trend in magnitude of |?SoHAT| for reactions with TEMPO, RuII(acac)2(py-imH) << [FeII(H2bip)3]2+ = [FeII(H2bim)3]2+ < [CoII(H2bim)3]2+, is surprisingly well predicted by the trends for electron transfer half-reaction entropies, ?SoET, in aprotic solvents. This is because both ?SoET and ?SoHAT have substantial contributions from vibrational entropy, which varies significantly with the metal center involved. The close connection between ?SoHAT and ?SoET provides an important link between these two fields and provides a starting point from which to predict which HAT systems will have important ground-state entropy effects. PMID:19275235

  4. Concentration of Hydrogen Peroxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2006-01-01

    Methods for concentrating hydrogen peroxide solutions have been described. The methods utilize a polymeric membrane separating a hydrogen peroxide solution from a sweep gas or permeate. The membrane is selective to the permeability of water over the permeability of hydrogen peroxide, thereby facilitating the concentration of the hydrogen peroxide solution through the transport of water through the membrane to the permeate. By utilizing methods in accordance with the invention, hydrogen peroxide solutions of up to 85% by volume or higher may be generated at a point of use without storing substantial quantities of the highly concentrated solutions and without requiring temperatures that would produce explosive mixtures of hydrogen peroxide vapors.

  5. Supported transition metal catalysts for para- to ortho-hydrogen conversion

    NASA Technical Reports Server (NTRS)

    Brooks, Christopher J.; Wang, Wei; Eyman, Darrell P.

    1994-01-01

    The main goal of this study was to develop and improve on existing catalysts for the conversion of ortho- to para-hydrogen. Starting with a commercially available Air Products nickel silicate, which had a beta value of 20, we were trying to synthesize catalysts that would be an improvement to AP. This was accomplished by preparing silicates with various metals as well as different preparation methods. We also prepared supported ruthenium catalysts by various techniques using several metal precursors to improve present technology. What was also found was that the activation conditions prior to catalytic testing was highly important for both the silicates and the supported ruthenium catalysts. While not the initial focus of the research, we made some interesting observations into the adsorption of H2 on ruthenium. This helped us to get a better understanding of how ortho- to para-H2 conversion takes place, and what features in a catalyst are important to optimize activity. Reactor design was the final area in which some interesting conclusions were drawn. As discussed earlier, the reactor catalyst bed must be constructed using straight 1/8 feet OD stainless steel tubing. It was determined that the use of 1/4 feet OD tubing caused two problems. First, the radius from the center of the bed to the wall was too great for thermal equilibrium. Since the reaction of ortho- to para-H2 is exothermic, the catalyst bed center was warmer than the edges. Second, the catalyst bed was too shallow using a 1/4 feet tube. This caused reactant blow-by which was thought to decrease the measured activity when the flow rate was increased. The 1/8 feet tube corrected both of these concerns.

  6. Metal aminoboranes

    DOEpatents

    Burrell, Anthony K.; Davis, Benjamin J.; Thorn, David L.; Gordon, John C.; Baker, R. Thomas; Semelsberger, Troy Allen; Tumas, William; Diyabalanage, Himashinie Vichalya Kaviraj; Shrestha, Roshan P.

    2010-05-11

    Metal aminoboranes of the formula M(NH.sub.2BH.sub.3).sub.n have been synthesized. Metal aminoboranes are hydrogen storage materials. Metal aminoboranes are also precursors for synthesizing other metal aminoboranes. Metal aminoboranes can be dehydrogenated to form hydrogen and a reaction product. The reaction product can react with hydrogen to form a hydrogen storage material. Metal aminoboranes can be included in a kit.

  7. Nature of water and hydrogen reactions on transition metal surfaces studied by scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Tatarkhanov, Mouslim Magomedovich

    Scanning Tunneling Microscopy (STM) has already been established as a tool for the investigation of simple reaction mechanisms. In this work I present results of two parallel studies using STM: first, hydrogen on Ru(0001) surface and second, water on Ru(0001) and Pd(111). In both studies initial stages of adsorption up to saturation monolayer coverage were investigated by variable temperature scanning tunneling microscopy (VT STM). The first step of the hydrogen adsorption study was the identification and characterization of the various coverage structures on clean Ru(0001). Hydrogen was found to adsorb dissociatively forming ( 3x3 )R30, 3 domains of (2x1), (2x2)-3H and (1x1) for increasing coverages of theta=0.3 ML, 0.5 ML, 0.75 ML and 0.1 ML respectively. Some of these structures were observed to coexist at intermediate coverage values. In addition effects of impurities such as oxygen and carbon on hydrogen adsorption has been discussed. Next, near saturation coverage the interesting mechanism of how H 2 dissociates and binds to the surface of Ru(0001) has been observed. We found that the H2 dissociation takes place only on Ru sites where the metal atom is not bound to any H atom. Such active sites are formed when at least 3 H-vacancies aggregate by thermal diffusion. Sites formed by single H-vacancies (i.e. unoccupied Ru sites) or pairs of adjoining vacancies were found to be unreactive toward H2. H-vacancies were observed as single entities diffusing on the surface at 50 K and able to form transient triangular shaped aggregations where H2 molecules dissociated. It was found that the diffusion and aggregation of the H-vacancies is essential in creation of active sites where dissociative adsorption of hydrogen occurs. The first step of water studies was the initial stages of growth of water on the hexagonal surfaces of Pd(111) and Ru(0001) in the temperature range between 40 K and 130 K. In addition, DFT calculations and STM image simulations were used to validate the models. Below 130 K water dissociation does not occur at any appreciable rate and only molecular films are formed. At these temperatures the kinetics of water growth leads to structures where the molecules bind to the metal substrate through the O-lone pair while making 3 H-bonds with neighboring molecules and form clusters of hexagonal units with a honeycomb structure. This bonding geometry imposes limitations to the size of the clusters, with unsaturated H-bonds confined to the cluster periphery. It is found that growth proceeds by attachement of water molecules to the edge of the clusters by H-bonds. These molecules bind only weakly to the metal substrate and can hop around the edges. Comparison of DFT and STM image calculations with experiments shows that on Pd the edge-attached molecules form two different structures, a metastable one where the molecule is elevated by 2.7 A with respect to the cluster molecules, and another where they are elevated by only 0.4 A. On Ru only the less elevated (0.4 A higher) edge-attached molecules are observed. In next final step, water structures on Ru(0001) were studied at temperatures above 140K. STM findings were backed by x-ray absorption spectroscopy. Additional DFT calculations and STM simulations provided validation of proposed models. It was found that while undissociated water layers are metastable below 140 K, heating above this temperature produces drastic transformations whereby a fraction of the water molecules partially dissociate and form mixed H 2O-OH structures. XPS and XAS revealed the presence of hydroxyl groups with their O-H bond essentiallymostly parallel to the surface. STM images show that the mixed H2O-OH structures consist of long narrow stripes aligned with the three crystallographic directions perpendicular to the close-packed atomic rows of the Ru(0001) substrate. The internal structure of the stripes is a honeycomb network of H-bonded water and hydroxyl species. We found that the metastable low temperature molecular phase can also be converted to a mixed H2O-OH phase through excitation

  8. Functionalization of Carbon-Hydrogen Bonds Through Transition Metal Carbenoid Insertion

    NASA Astrophysics Data System (ADS)

    Davies, Huw M. L.; Dick, Allison R.

    The functionalization of carbon-hydrogen bonds through transition metal carbenoid insertion is becoming a powerful method for the construction of new carbon-carbon bonds in organic synthesis. This chapter will highlight recent developments in this field, while placing it within its historical context. Intramolecular carbenoid C-H insertion will be covered first, focusing on formation of three- and six-membered rings, as well as the use of nontraditional substrates. Additionally, the most recent progress in asymmetric catalysis will be discussed. The bulk of the chapter will concentrate on intermolecular transformations, emphasizing both the effect of substrate structure and the influence of carbene substituent electronics on the regioselectivity of the reactions. Vinyldiazoacetates will be covered as a distinct class of carbenoid precursor, as they have been shown to initiate a variety of unique transformations, such as the combined C-H activation/Cope rearrangement. Finally, the synthetic utility of carbenoid C-H insertion reactions, both intra- and intermolecular, will be displayed through their use in the total syntheses of a number of natural products and pharmaceuticals.

  9. Hydrogen storage properties of metal nitroprussides M[Fe(CN)5NO], (M = Co, Ni)

    SciTech Connect

    Culp, J.T.; Matranga, C.S.; Smith, M.; Bittner, E.W.; Bockrath, B.C.

    2006-04-27

    The volumetric hydrogen adsorption isotherms of two isostructural dehydrated cubic metal nitroprussides M[Fe(CN)5NO] (M = Co2+, Ni2+) have been measured up to a pressure of 760 Torr at 77 and 87 K. These materials are among the most efficient H2 sorbents based on porous coordination polymers reported to date. The H2 uptake in both materials is ?1.6 wt % at 77 K and 760 torr. These H2 capacities match those reported recently in the structurally related M3[Co(CN)6]2 compounds and are approximately 25% higher than those reported for Zn4O(1,4-benzenedicarboxylate)3 under the same conditions of temperature and pressure. The isosteric heats of H2 adsorption calculated from the 77 and 87 K isotherms for both materials were found to vary from ?7.5 kJ/mol at 0.40 wt % coverage to ?5.5 kJ/mol at 1.2 wt % coverage. The N2 BET surface areas were determined to be 634 m2/g and 523 m2/g for M = Ni and M = Co, respectively.

  10. The sorption of hydrogen sulfide from hot syngas by metal oxides over supports.

    PubMed

    Ko, Tzu-Hsing; Chu, Hsin; Chaung, Lung-Kai

    2005-01-01

    Six 5 wt.% metal sorbents including Mn, Fe, Cu, Co, Ce and Zn supported on gamma-Al2O3, prepared by the incipient wetness impregnation method with calcination at 700 degrees C for 2 h, have been investigated for sorption of hydrogen sulfide in the temperature range of 500-700 degrees C. The sorption experiments were conducted in a fixed-bed reactor in terms of breakthrough curves and characterized by X-ray powder diffraction. The results reveal that the copper and manganese sorbents exhibit the best performance because they provide nearly 100% utilization, but the copper sorbent has a lower sulfur sorption capacity compared with the manganese sorbent. The zinc and cerium sorbents are not good candidates attributed to the vaporization of zinc and unexpected product for cerium. Effects of support materials on 5 wt.% manganese were also investigated by using gamma-Al2O3, SiO2 and TiO2 in this study. Five weight percent Mn/gamma-Al2O3 shows the best performance among support candidates. On the basis of XRPD and BET surface area analysis, TiO2 appears a huge loss in BET surface area associated with a significant formation of rutile form. PMID:15620738

  11. Tristate electrochemical metallization memory based in the hydrogenated nanocrystalline silicon films

    SciTech Connect

    Yan, X. B.; Chen, Y. F.; Hao, H.; Zhang, E. P.; Shi, S. S.; Lou, J. Z.; Liu, Q.

    2014-08-18

    The hydrogenated nanocrystalline silicon (nc-Si:H) films have been fabricated as resistive switching medium by radio frequency plasma enhanced chemical vapor deposition technology. The constructed Ag/nc-Si:H/Pt structure exhibits stable three nonvolatile resistance states. Tristate resistive states with large ratio 10{sup 2} and 10{sup 5}, less variation of resistance, and long retention exceeding 2.3 × 10{sup 5 }s are observed in Ag/nc-Si:H/Pt stack. The temperature dependence of high resistance state (HRS) and intermediate resistance state (IRS) both show semiconductor behavior, and the temperature dependence of low resistance state (LRS) represents metallic property. Fitting results demonstrated that the conduction mechanism of HRS, IRS, and LRS showed space charge limited conduction (SCLC), tunneling, and ohmic characteristics, respectively. The discrete Ag filament with Si nanocrystalline and complete Ag filament is proposed to be responsible for the performance IRS and LRS. We supposed that the Ag{sup +} ions prefer to be reduced to Ag atoms near the Si nanocrystalline location. Si nanocrystalline between Ag nanoparticles contribute to the current transport at IRS.

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

    PubMed

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

    2015-07-21

    Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an overpotential of 1.0 V, without apparent loss in activity. Replacing the oxo moiety with a disulfide affords [(PY5Me2)MoS2](2+), which bears a molecular MoS2 triangle that structurally and functionally mimics bulk molybdenum disulfide, improving the catalytic activity for water reduction. In water buffered to pH 3, catalysis by [(PY5Me2)MoS2](2+) onsets at 400 mV of overpotential, whereas [(PY5Me2)MoO](2+) requires an additional 300 mV of driving force to operate at the same current density. Metalation of the PY5Me2 ligand with an appropriate Co(ii) source also furnishes electrocatalysts that are active in water. Importantly, the onset of catalysis by the [(PY5Me2)Co(H2O)](2+) series is anodically shifted by introducing electron-withdrawing functional groups on the ligand. With the [(bpy2PYMe)Co(CF3SO3)](1+) system, we showed that introducing a redox-active moiety can facilitate the electro- and photochemical reduction of protons from weak acids such as acetic acid or water. Using a high-throughput photochemical reactor, we examined the structure-reactivity relationship of a series of cobalt(ii) complexes. Taken together, these findings set the stage for the broader application of polypyridyl systems to catalysis under environmentally benign aqueous conditions. PMID:26101803

  13. Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

    PubMed

    Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

    2015-10-27

    The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability. PMID:26418767

  14. A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces

    SciTech Connect

    Liu P.; Yang, Y.; White, M.G.

    2012-01-12

    Density functional theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations were employed to investigate the methanol synthesis reaction from CO{sub 2} hydrogenation (CO{sub 2} + 3H{sub 2} {yields} CH{sub 3}OH + H{sub 2}O) on metal-doped Cu(111) surfaces. Both the formate pathway and the reverse water-gas shift (RWGS) reaction followed by a CO hydrogenation pathway (RWGS + CO-Hydro) were considered in the study. Our calculations showed that the overall methanol yield increased in the sequence: Au/Cu(111) < Cu(111) < Pd/Cu(111) < Rh/Cu(111) < Pt/Cu(111) < Ni/Cu(111). On Au/Cu(111) and Cu(111), the formate pathway dominates the methanol production. Doping Au does not help the methanol synthesis on Cu(111). Pd, Rh, Pt, and Ni are able to promote the methanol production on Cu(111), where the conversion via the RWGS + CO-Hydro pathway is much faster than that via the formate pathway. Further kinetic analysis revealed that the methanol yield on Cu(111) was controlled by three factors: the dioxomethylene hydrogenation barrier, the CO binding energy, and the CO hydrogenation barrier. Accordingly, two possible descriptors are identified which can be used to describe the catalytic activity of Cu-based catalysts toward methanol synthesis. One is the activation barrier of dioxomethylene hydrogenation, and the other is the CO binding energy. An ideal Cu-based catalyst for the methanol synthesis via CO{sub 2} hydrogenation should be able to hydrogenate dioxomethylene easily and bond CO moderately, being strong enough to favor the desired CO hydrogenation rather than CO desorption but weak enough to prevent CO poisoning. In this way, the methanol production via both the formate and the RWGS + CO-Hydro pathways can be facilitated.

  15. Evaluation of Metal Halide, Plasma, and LED Lighting Technologies for a Hydrogen Fuel Cell Mobile Light (H 2 LT)

    DOE PAGESBeta

    Miller, L. B.; Donohoe, S. P.; Jones, M. H.; White, W. A.; Klebanoff, L. E.; Velinsky, S. A.

    2015-04-22

    This article reports on the testing and comparison of a prototype hydrogen fuel cell light tower (H2LT) and a conventional diesel-powered metal halide light trailer for use in road maintenance and construction activities. The prototype was originally outfitted with plasma lights and then with light-emitting diode (LED) luminaires. Light output and distribution, lighting energy efficiency (i.e., efficacy), power source thermal efficiency, and fuel costs are compared. The metal halide luminaires have 2.2 and 3.1 times more light output than the plasma and LED luminaires, respectively, but they require more power/lumen to provide that output. The LED luminaires have 1.6 timesmore » better light efficacy than either the metal halide or plasma luminaires. The light uniformity ratios produced by the plasma and LED towers are acceptable. The fuel cell thermal efficiency at the power required to operate the plasma lights is 48%, significantly higher than the diesel generator efficiency of 23% when operating the metal halide lights. Due to the increased efficiency of the fuel cell and the LED lighting, the fuel cost per lumen-hour of the H2LT is 62% of the metal halide diesel light tower assuming a kilogram of hydrogen is twice the cost of a gallon of diesel fuel.« less

  16. Hydrogen incorporation induced metal-semiconductor transition in ZnO:H thin films sputtered at room temperature

    SciTech Connect

    Singh, Anil; Chaudhary, Sujeet; Pandya, D. K.

    2013-04-29

    The room temperature deposited ZnO:H thin films having high conductivity of 500 Ohm-Sign {sup -1} cm{sup -1} and carrier concentration reaching 1.23 Multiplication-Sign 10{sup 20} cm{sup -3} were reactively sputter deposited on glass substrates in the presence of O{sub 2} and 5% H{sub 2} in Ar. A metal-semiconductor transition at 165 K is induced by the increasing hydrogen incorporation in the films. Hydrogen forms shallow donor complex with activation energy of {approx}10-20 meV at oxygen vacancies (V{sub O}) leading to increase in carrier concentration. Hydrogen also passivates V{sub O} and V{sub Zn} causing {approx}4 times enhancement of mobility to 25.4 cm{sup 2}/V s. These films have potential for use in transparent flexible electronics.

  17. Roles of hydrogenation, annealing and field in the structure and magnetic entropy change of Tb-based bulk metallic glasses

    NASA Astrophysics Data System (ADS)

    Luo, Qiang; Schwarz, Bjrn; Mattern, Norbert; Shen, Jun; Eckert, Jrgen

    2013-03-01

    The reduction of open-volume regions in Tb-based metallic glass (MG) by annealing and hydrogen charging was found to rearrange the atomic structure and tune the magnetic behaviors. After crystallization, the magnetic structure and magnetic entropy change (MEC) alters due to the structural transformation, and a plateau-like-MEC behavior can be obtained. The hydrogen concentration after charging at 1mA/cm2 for 576 h reaches as high as 3290 w-ppm. The magnetization behavior and the MEC change due to the modification of the exchange interaction and the random magnetic anisotropy (RMA) upon hydrogenation. At low temperatures, irreversible positive MEC was obtained, which is related to the internal entropy production. The RMA-to-exchange ratio acts as a switch to control the irreversible entropy production channel and the reversible entropy transfer channel. The field dependence of the MEC is discussed in term of the competition among Zeeman energy, exchange interaction and RMA.

  18. Insights on Hydrogen Liberation from Water Using Anionic Transition Metal Oxide Clusters: a Combined Computational and Spectroscopic Study

    NASA Astrophysics Data System (ADS)

    Ramabhadran, Raghunath O.; Mann, Jenniffer E.; Waller, Sarah. E.; Rothgeb, David W.; Jarrold, Caroline C.; Raghavachari, Krishnan

    2013-06-01

    Transition Metal Oxides (TMOs) offer widespread applications in catalysis and the generation of alternate sources of energy. Cluster models are useful to model the defect sites in these TMO surfaces which are responsible for their catalytic activities. In this combined computational (DFT) and spectroscopic (PES/MS) study, we present the interesting features in the chemical reactions of molybdenum oxide and tungsten oxide clusters with water. The results obtained provide valuable insights on the roles played by differing metal-oxygen bond strengths, the initial electrostatic complex formed and the geometric factors involved in the liberation of hydrogen gas from water.

  19. N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions.

    PubMed

    Zhang, Jintao; Qu, Liangti; Shi, Gaoquan; Liu, Jiangyong; Chen, Jianfeng; Dai, Liming

    2016-02-01

    The high cost and scarcity of noble metal catalysts, such as Pt, have hindered the hydrogen production from electrochemical water splitting, the oxygen reduction in fuel cells and batteries. Herein, we developed a simple template-free approach to three-dimensional porous carbon networks codoped with nitrogen and phosphorus by pyrolysis of a supermolecular aggregate of self-assembled melamine, phytic acid, and graphene oxide (MPSA/GO). The pyrolyzed MPSA/GO acted as the first metal-free bifunctional catalyst with high activities for both oxygen reduction and hydrogen evolution. Zn-air batteries with the pyrolyzed MPSA/GO air electrode showed a high peak power density (310 W g(-1) ) and an excellent durability. Thus, the pyrolyzed MPSA/GO is a promising bifunctional catalyst for renewable energy technologies, particularly regenerative fuel cells. PMID:26709954

  20. Effect of electrolytical hydrogenation on the thermal stability and crystallization kinetics of metallic glass Fe79Si9B12

    NASA Astrophysics Data System (ADS)

    Grecki, Cz; Grecki, T.

    2011-04-01

    The effect of electrolytical hydrogenation on both the surface and volume crystallization kinetics and thermal stability of amorphous alloy Fe79Si9B12 has been investigated. The parameters of the surface and volume crystallization (temperature, activation energy) have been determined applying the exoelectron emission (EEE) and differential thermal analysis (DTA) methods, respectively. It has been found that the surface crystallization of investigated material occurs at temperature much lower and with activation energy smaller than the volume crystallization. The determination of the activation energies for the volume and surface crystallization by the combination of DTA and EEE techniques enables the determination of activation energies for both the nucleation and growth of the crystalline phase in metallic glasses and other amorphous materials. Hydrogenation of the investigated metallic glass reduces its thermal stability, what is manifested by an decrease in the activation energies for both the surface and volume crystallization.